CN103000903A

CN103000903A - Precursor doped with carbon nanomaterial and preparation method thereof as well as spherical lithium metal oxide anode material and preparation method thereof

Info

Publication number: CN103000903A
Application number: CN2012104947389A
Authority: CN
Inventors: 杜春雨; 盛夏; 陈猛; 尹鸽平; 左朋建; 程新群; 马玉林
Original assignee: Harbin Institute of Technology
Current assignee: Harbin Institute of Technology
Priority date: 2012-11-28
Filing date: 2012-11-28
Publication date: 2013-03-27
Anticipated expiration: 2032-11-28
Also published as: CN103000903B

Abstract

The invention discloses a precursor doped with a carbon nanomaterial and a preparation method thereof as well as a spherical lithium metal oxide anode material and a preparation method thereof, and relates to the precursor and the preparation method thereof as well as the lithium metal oxide anode material and the preparation method thereof. The invention aims at solving the problems of great initial irreversible capacity loss, poor rate capability and low tap density of the existing lithium metal oxide anode material due to the fact that the precursor for perfecting the lithium metal oxide anode material cannot be prepared by the prior art. The precursor is the metal oxide anode or metal carbonate doped with the carbon nanomaterial. The method comprises the steps of firstly preparing a metal ion material, orderly preparing mixed metal ion salt solution, a precipitator, a complexing agent, and carbon nanomaterial suspension liquid, then carrying out co-precipitation reaction, and carrying out washing and drying treatment. The spherical lithium metal oxide anode material is prepared from lithium compound and the precursor doped with the carbon nanomaterial. The method comprises the steps of firstly, processing the precursor in advance, mixing with lithium and then sintering.

Description

A kind of presoma of doping carbon nano material and preparation method and spherical lithium metal oxide positive electrode and preparation method

Technical field

The present invention relates to a kind of presoma and preparation method and lithium metal oxide positive electrode and preparation method.

Background technology

Lithium ion battery is high because of voltage platform, energy density is large, memory-less effect, the advantage such as have extended cycle life, and becomes gradually the substitute of the batteries such as ni-mh, NI-G, plumbic acid, and is widely used in the multiple fields such as daily life, industry, military affairs.Positive electrode is the key factor that determines the performances such as lithium ion battery energy density, useful life and fail safe.The anode material for lithium-ion batteries of using in batches in the market mainly contains cobalt acid lithium, LiMn2O4, LiFePO4 etc.The structure of cobalt acid lithium is more stable, is a kind of very ripe positive electrode, occupies at present the leading position of positive electrode, but its resource-constrained, expensive, have problem of environmental pollution, and its useful life is shorter, fail safe is very poor, development is restricted.LiMn2O4 has the advantages such as aboundresources, low price, fail safe are good, but its cyclical stability is poor, bad with the electrolyte compatibility.The advantages such as that LiFePO 4 material has is nontoxic, pollution-free, security performance is good, raw material wide material sources, life-span are long, but its tap density is lower, poorly conductive, lithium ion diffusion velocity are slow.And, the theoretical capacity of this different materials is not very high, its actual capacity also more is lower than 150mAh/g, and this has limited the energy density of lithium ion battery to a great extent, thereby has restricted the application of lithium ion battery in fields such as portable electric appts and electric automobiles.

Possess in recent years that capacity is high, the polynary transition metal embedding oxidate for lithium Li such as nickel cobalt manganese of good cycling stability and the multiple advantage such as low-cost _1+xMn _αCo _βNi _γM _yO ₂(wherein M is one or more among Cr, Al, Fe, Mg, Ag, Ti, Cu, V, Y, La, Tm, Gd, Ho, Ce, Lu, Yb, the Sc, and alpha+beta+γ+y=1,0＜α≤1,0≤β≤1,0≤γ≤1,0≤x≤0.34,0≤y≤0.5, β and γ are not zero simultaneously) just attracting the extensive concern of Chinese scholars and research and development institution.The polynary transition metal embedding oxidate for lithium Li such as nickel cobalt manganese _1+xMn _αCo _βNi _γM _yO ₂During middle x=0, be three common metaclass materials.This material is owing to the cooperative effect between transition metal, and chemical property is better than arbitrary one-component oxide.Calendar year 2001 OhZuku and Makimura have synthesized the trielement composite material LiNi of Ni:Co:Mn=1:1:1 first _1/3Co _1/3Mn _1/3O ₂, Canadian Dahn of while etc. has studied change of component to LiMn _αCo _βNi _γO ₂The impact of trielement composite material crystal structure, capacity, high rate performance and thermal stability.There is obvious trielement synergistic effect in such material: introduce the Co element, can effectively reduce lithium nickel ion mixing phenomenon, the layer structure of stabilizing material; Introduce the Ni element, can significantly improve the specific capacity of material; Introduce the Mn element, not only can reduce cost, but also can improve the fail safe stability of material.In addition, studies show that the metals such as mix a small amount of Al, Ti can further improve the performances such as the multiplying power of polynary transition metal embedding oxidate for lithium material and cycle life.

As polynary transition metal embedding oxidate for lithium Li such as above-mentioned nickel cobalt manganese _1+xMn _αCo _βNi _γM _yO ₂Middle x＞0 o'clock is also referred to as rich lithium material, and this molecular formula also can be rewritten as xLi ₂MnO ₃(1-x) LiM _aO ₂, LiM wherein _aO ₂Transition metal embedding oxidate for lithium LiMn _α`Co _β`Ni _γ`O ₂In (0＜α `≤1,0≤β `≤1,0≤γ `≤1, β `+ γ ` 〉=0) or its metal-doped material one or more.Rich lithium material is the class positive electrode that the researcher of Argonne National Laboratory of USDOE develops, and this material list reveals very high specific capacity, surpasses 250mAh/g, near 2 times of traditional anode material for lithium-ion batteries capacity.And, substitute the cost that expensive cobalt, nickel can reduce lithium ion battery greatly with manganese base lithium-rich anode material.In addition, rich lithium material also has the advantages such as the higher and production technology of fail safe is simple.Therefore, rich lithium material is a kind of positive electrode that has a extensive future, adopt the lithium ion battery of rich lithium material to obtain extensive use in a series of fields, comprise the consumption electronic products such as mobile phone, notebook computer, the medical apparatus such as wireless tool and cardiac pacemaker, defibrillator, and electric automobile and hybrid vehicle etc.

But, be that polynary transition metal embedding oxidate for lithium or rich lithium material all exist the problems such as irreversible capacity loss is large first, high rate performance is relatively poor.And, to compare with the commercial cobalt acid lithium material of maturation, also there is the lower problem of tap density in this two classes material.These problems have seriously hindered the practicalization of polynary transition metal embedding oxidate for lithium and rich lithium material.Therefore, prior art can't be prepared the presoma that improves polynary transition metal embedding oxidate for lithium and rich lithium material performance, and there are the problem that irreversible capacity loss is large first, high rate performance is relatively poor and tap density is lower in the polynary transition metal embedding oxidate for lithium or the rich lithium material that cause existing method to prepare.

Summary of the invention

The objective of the invention is to solve prior art and can't prepare the presoma that improves the lithium metal oxide positive electrode, cause existing lithium metal oxide positive electrode to have the problem that irreversible capacity loss is large first, high rate performance is relatively poor and tap density is lower; And provide a kind of presoma and preparation method and spherical lithium metal oxide positive electrode and preparation method of doping carbon nano material.

A kind of presoma of doping carbon nano material is that Uniform Doped carbon nanomaterial, molecular formula are Mn _αCo _βNi _γM _y(OH) ₂Metal hydroxides or Uniform Doped carbon nanomaterial, molecular formula be Mn _αCo _βNi _γM _yCO ₃Metal carbonate; Wherein said Mn _αCo _βNi _γM _y(OH) ₂In 0＜α≤1,0≤β≤1,0≤γ≤1,0≤y≤0.5, and alpha+beta+γ+y=1, β+γ＞0, described Mn _αCo _βNi _γM _y(OH) ₂Middle M is a kind of or wherein several among Cr, Al, Fe, Mg, Ag, Ti, Cu, V, Y, La, Tm, Gd, Ho, Ce, Lu, Yb and the Sc; Wherein said Mn _αCo _βNi _γM _yCO ₃In 0＜α≤1,0≤β≤1,0≤γ≤1,0≤y≤0.5, and alpha+beta+γ+y=1, β+γ＞0, described Mn _αCo _βNi _γM _yCO ₃Middle M is a kind of or wherein several among Cr, Al, Fe, Mg, Ag, Ti, Cu, V, Y, La, Tm, Gd, Ho, Ce, Lu, Yb and the Sc.

A kind of preparation method of presoma of doping carbon nano material specifically finishes: one, prepare raw material: according to chemical formula Mn according to the following steps _αCo _βNi _γM _y(OH) ₂By the Mn element: Co element: Ni element: M element mol ratio is that α: β: γ: y prepares soluble manganese salt, solubility cobalt salt, soluble nickel salt and soluble M salt; Two, preparation hybrid metal ion salt solution: soluble manganese salt, solubility cobalt salt, soluble nickel salt and soluble M salt that step 1 is prepared join in the solvent and mix, and being configured to the hybrid metal ion concentration is the hybrid metal ion salt solution of 0.01mol/L ~ 5mol/L; Three, preparation precipitation reagent: solubility hydroxide is added in the solvent, be configured to OH ^-Concentration is 0.1mol/L ~ 10mol/L precipitation reagent; Four, preparation complexing agent: solubility ammonium salt or ammoniacal liquor are added in the solvent, be configured to NH ₄ ⁺Concentration is 0.1mol/L ~ 10mol/L complexing agent; Five, preparation carbon nanomaterial suspension: carbon nanomaterial is scattered in the solvent, and being configured to carbon nanomaterial concentration is the carbon nanomaterial suspension of 0.1mg/L ~ 50g/L; Six, coprecipitation reaction: the hybrid metal ion concentration that step 2 is prepared is the hybrid metal ion salt solution of 0.01mol/L ~ 5mol/L, the OH of step 3 preparation ^-Concentration is the NH of 0.1mol/L ~ 10mol/L precipitation reagent, step 4 preparation ₄ ⁺Concentration is that the carbon nanomaterial concentration of 0.1mol/L ~ 10mol/L complexing agent and step 5 preparation is that the carbon nanomaterial suspension of 0.1mg/L ~ 50g/L adds in the reactor that the reaction initial soln is housed simultaneously, the hybrid metal ion concentration of step 2 preparation is that the adding speed of the hybrid metal ion salt solution of 0.01mol/L ~ 5mol/L is 0.1mL/min ~ 1000mL/min, the OH-concentration of step 3 preparation is that the adding speed of 0.1mol/L ~ 10mol/L precipitation reagent is 0.1mL/min ~ 1000mL/min, the NH4+ concentration of step 4 preparation is that the adding speed of 0.1mol/L ~ 10mol/L complexing agent is 0.1mL/min ~ 1000mL/min, the carbon nanomaterial concentration of step 5 preparation is that the adding speed of the carbon nanomaterial suspension of 0.1mg/L ~ 50g/L is 0.1mL/min ~ 500mL/min, and it is 20 ℃ ~ 90 ℃ in temperature, mixing speed is 100rpm ~ 10000rpm, pH be 5 ~ 13 and inert gas shielding under react, namely obtain the spherical precipitation thing; Seven, washing is dry processes: the spherical precipitation thing that at first adopts the washed with de-ionized water step 6 to obtain, clean be neutrality to the pH of filtrate till, then be 20 ℃ ~ 150 ℃ in temperature and be dried to constant weight, namely obtain the Uniform Doped carbon nanomaterial, molecular formula is Mn _αCo _βNi _γM _y(OH) ₂Metal hydroxides; Described Mn described in the step 1 _αCo _βNi _γM _y(OH) ₂In 0＜α≤1,0≤β≤1,0≤γ≤1,0≤y≤0.5, and alpha+beta+γ+y=1, β+γ＞0, wherein said Mn _αCo _βNi _γM _y(OH) ₂Middle M is a kind of or wherein several among Cr, Al, Fe, Mg, Ag, Ti, Cu, V, Y, La, Tm, Gd, Ho, Ce, Lu, Yb and the Sc; The volume of the reaction initial soln described in the step 6 and the volumetric ratio of reactor are (0.001 ~ 0.8): 1.

A kind of preparation method of presoma of doping carbon nano material specifically finishes: one, prepare raw material: according to chemical formula Mn according to the following steps _αCo _βNi _γM _yCO ₃By the Mn element: Co element: Ni element: M element mol ratio is that α: β: γ: y prepares soluble manganese salt, solubility cobalt salt, soluble nickel salt and soluble M salt; Two, preparation hybrid metal ion salt solution: soluble manganese salt, solubility cobalt salt, soluble nickel salt and soluble M salt that step 1 is prepared join in the solvent and mix, and being configured to the hybrid metal ion concentration is the hybrid metal ion salt solution of 0.01mol/L ~ 5mol/L; Three, preparation precipitation reagent: solubility hydroxide is added in the solvent, be configured to CO ₃ ^2-Concentration is 0.1mol/L ~ 10mol/L precipitation reagent; Four, preparation complexing agent: solubility ammonium salt or ammoniacal liquor are added in the solvent, be configured to NH ₄ ⁺Concentration is 0.1mol/L ~ 10mol/L complexing agent; Five, preparation carbon nanomaterial suspension: carbon nanomaterial is scattered in the solvent, and being configured to carbon nanomaterial concentration is the carbon nanomaterial suspension of 0.1mg/L ~ 50g/L; Six, coprecipitation reaction: the hybrid metal ion concentration that step 2 is prepared is the hybrid metal ion salt solution of 0.01mol/L ~ 5mol/L, the CO of step 3 preparation ₃ ^2-Concentration is the NH of 0.1mol/L ~ 10mol/L precipitation reagent, step 4 preparation ₄ ⁺Concentration is that the carbon nanomaterial concentration of 0.1mol/L ~ 10mol/L complexing agent and step 5 preparation is that the carbon nanomaterial suspension of 0.1mg/L ~ 50g/L adds in the reactor that the reaction initial soln is housed simultaneously, the hybrid metal ion concentration of step 2 preparation is that the adding speed of the hybrid metal ion salt solution of 0.01mol/L ~ 5mol/L is 0.1mL/min ~ 1000mL/min, the CO of step 3 preparation ₃ ^2-Concentration is that the adding speed of 0.1mol/L ~ 10mol/L precipitation reagent is 0.1mL/min ~ 1000mL/min, the NH of step 4 preparation ₄ ⁺Concentration is that the adding speed of 0.1mol/L ~ 10mol/L complexing agent is 0.1mL/min ~ 1000mL/min, the carbon nanomaterial concentration of step 5 preparation is that the adding speed of the carbon nanomaterial suspension of 0.1mg/L ~ 50g/L is 0.1mL/min ~ 500mL/min, and temperature be 20 ℃ ~ 90 ℃, mixing speed be 100rpm ~ 10000rpm, pH be 5 ~ 13 and inert gas shielding under react, namely obtain the spherical precipitation thing; Seven, washing is dry processes: the spherical precipitation thing that at first adopts the washed with de-ionized water step 6 to obtain, clean be neutrality to the pH of filtrate till, then be 20 ℃ ~ 150 ℃ in temperature and be dried to constant weight, namely obtain the Uniform Doped carbon nanomaterial, molecular formula is Mn _αCo _βNi _γM _yCO ₃Metal carbonate; Described Mn described in the step 1 _αCo _βNi _γM _yCO ₃In 0＜α≤1,0≤β≤1,0≤γ≤1,0≤y≤0.5, and alpha+beta+γ+y=1, β+γ＞0, wherein said Mn _αCo _βNi _γM _yCO ₃Middle M is a kind of or wherein several among Cr, Al, Fe, Mg, Ag, Ti, Cu, V, Y, La, Tm, Gd, Ho, Ce, Lu, Yb and the Sc; The volume of the reaction initial soln described in the step 6 and the volumetric ratio of reactor are (0.001 ~ 0.8): 1.

A kind of spherical lithium metal oxide positive electrode is prepared from by the presoma of lithium-containing compound and above-mentioned doping carbon nano material; The ratio of the amount of the Li elemental substance in the presoma of described doping carbon nano material in the total amount of substance of metallic element and the described lithium-containing compound is 1:(1 ~ 1.42); The presoma of described doping carbon nano material is that Uniform Doped carbon nanomaterial, molecular formula are Mn _αCo _βNi _γM _y(OH) ₂Metal hydroxides or Uniform Doped carbon nanomaterial, molecular formula be Mn _αCo _βNi _γM _yCO ₃Metal carbonate; Wherein said Mn _αCo _βNi _γM _y(OH) ₂In 0＜α≤1,0≤β≤1,0≤γ≤1,0≤y≤0.5, and alpha+beta+γ+y=1, β+γ＞0, described Mn _αCo _βNi _γM _y(OH) ₂Middle M is a kind of or wherein several among Cr, Al, Fe, Mg, Ag, Ti, Cu, V, Y, La, Tm, Gd, Ho, Ce, Lu, Yb and the Sc; Wherein said Mn _αCo _βNi _γM _yCO ₃In 0＜α≤1,0≤β≤1,0≤γ≤1,0≤y≤0.5, and alpha+beta+γ+y=1, β+γ＞0, described Mn _αCo _βNi _γM _yCO ₃Middle M is a kind of or wherein several among Cr, Al, Fe, Mg, Ag, Ti, Cu, V, Y, La, Tm, Gd, Ho, Ce, Lu, Yb and the Sc.

A kind of preparation method of spherical lithium metal oxide positive electrode, specifically finish according to the following steps: one, presoma preliminary treatment: the presoma of doping carbon nano material claimed in claim 1 at 200 ℃ ~ 800 ℃ pre-burning 1h ~ 12h, is obtained presoma after the preliminary treatment; Two, mixed lithium sintering: presoma after the preliminary treatment is mixed with lithium-containing compound, is 600 ℃ ~ 1200 ℃ roasting 3h ~ 36h in temperature then, cools to room temperature with the furnace and namely obtains spherical lithium metal oxide positive electrode; The presoma of the doping carbon nano material described in the step 1 is that Uniform Doped carbon nanomaterial, molecular formula are Mn _αCo _βNi _γM _y(OH) ₂Metal hydroxides or Uniform Doped carbon nanomaterial, molecular formula be Mn _αCo _βNi _γM _yCO ₃Metal carbonate; Wherein said Mn _αCo _βNi _γM _y(OH) ₂In 0＜α≤1,0≤β≤1,0≤γ≤1,0≤y≤0.5, y is: 0≤y≤0.5, and alpha+beta+γ+y=1, β+γ＞0, described Mn _αCo _βNi _γM _y(OH) ₂Middle M is a kind of or wherein several among Cr, Al, Fe, Mg, Ag, Ti, Cu, V, Y, La, Tm, Gd, Ho, Ce, Lu, Yb and the Sc; Wherein said Mn _αCo _βNi _γM _yCO ₃In 0＜α≤1,0≤β≤1,0≤γ≤1,0≤y≤0.5, y is: 0≤y≤0.5, and alpha+beta+γ+y=1, β+γ＞0, described Mn _αCo _βNi _γM _yCO ₃Middle M is a kind of or wherein several among Cr, Al, Fe, Mg, Ag, Ti, Cu, V, Y, La, Tm, Gd, Ho, Ce, Lu, Yb and the Sc; The ratio of the amount of the Li elemental substance in the presoma of the doping carbon nano material described in the step 1 in the total amount of substance of metallic element and the lithium-containing compound described in the step 2 is 1:(1 ~ 1.42).

Advantage of the present invention: one, the uniformity of the pyroreaction of the presoma of the doping carbon nano material of the present invention preparation in can the acceleration of sintering process, thereby suppress to a certain extent in the body phase lattice oxygen and deviate from the phenomenon that the room is occupied by transition metal ions, promote the spherical lithium metal oxide positive electrode first charge-discharge efficiency of the present invention's preparation, there are the first larger defective of irreversible capacity loss in the polynary transition metal embedding oxidate for lithium and the rich lithium material that have overcome existing method preparation; Two, the presoma of the doping carbon nano material of the present invention's preparation can impel the inner 3D of formation of material pore passage structure, therefore there is the 3D pore passage structure in the spherical lithium metal oxide positive electrode inside of the present invention's preparation, promote the diffusion of lithium ion at material internal, improved the high rate performance of material; Three, the presoma of the doping carbon nano material of the present invention's preparation can be regulated and control by the interpolation of carbon nanomaterial nucleation and the growth course of presoma, and then in conjunction with the optimization of synthesis condition, the spheric granules that the presoma pattern is homogeneous grain diameter can be controlled, the spherical lithium metal oxide positive electrode of high-tap density can be prepared thus; Four, to prepare the method technique of presoma of the method for spherical lithium metal oxide positive electrode and preparation doping carbon nano material simple in the present invention, and preparation cost is low, and with short production cycle, and the spherical lithium metal oxide positive electrode (Li that finally obtains _1+xMn _αCo _βNi _γM _yO ₂) steady quality, high power capacity, long circulation life and tap density be high.

Description of drawings

Fig. 1 is the XRD collection of illustrative plates of testing the presoma of a doping carbon nano material for preparing; Fig. 2 is the SEM figure that tests the presoma of a doping carbon nano material for preparing; Fig. 3 is the charging and discharging curve figure of the spherical lithium metal oxide positive electrode of test two preparations, A represents to test the spherical lithium metal oxide positive electrode charge graph of two preparations among the figure, and B represents to test the spherical lithium metal oxide anode material discharging curve chart of two preparations among the figure; Fig. 4 is high rate performance figure, among the figure A represent to test two preparations spherical lithium metal oxide positive electrodes high rate performance figure, B represents to test the high rate performance figure of the existing polynary transition metal embedding oxidate for lithiums of two preparations among the figure; Fig. 5 is the XRD collection of illustrative plates of testing the presoma of the three doping carbon nano materials that prepare; Fig. 6 is the SEM figure that tests the presoma of the three doping carbon nano materials that prepare; Fig. 7 is the SEM figure that tests the presoma of the five doping carbon nano materials that prepare; Fig. 8 is the spherical lithium metal oxide positive electrode XRD figure of test four preparations; Fig. 9 is that the spherical lithium metal oxide positive electrode of test four preparations amplifies 5000 times SEM figure; Figure 10 is that the presoma of the doping carbon nano material of test five preparations amplifies 5000 times SEM figure.

Embodiment

Embodiment one: present embodiment is a kind of presoma of doping carbon nano material, and the presoma of doping carbon nano material is that Uniform Doped carbon nanomaterial, molecular formula are Mn _αCo _βNi _γM _y(OH) ₂Metal hydroxides or Uniform Doped carbon nanomaterial, molecular formula be Mn _αCo _βNi _γM _yCO ₃Metal carbonate.

The described Mn of present embodiment _αCo _βNi _γM _y(OH) ₂In 0＜α≤1,0≤β≤1,0≤γ≤1,0≤y≤0.5, and alpha+beta+γ+y=1, β+γ＞0, described Mn _αCo _βNi _γM _y(OH) ₂Middle M is a kind of or wherein several among Cr, Al, Fe, Mg, Ag, Ti, Cu, V, Y, La, Tm, Gd, Ho, Ce, Lu, Yb and the Sc.

The described Mn of present embodiment _αCo _βNi _γM _yCO ₃In 0＜α≤1,0≤β≤1,0≤γ≤1,0≤y≤0.5, and alpha+beta+γ+y=1, β+γ＞0, described Mn _αCo _βNi _γM _yCO ₃Middle M is a kind of or wherein several among Cr, Al, Fe, Mg, Ag, Ti, Cu, V, Y, La, Tm, Gd, Ho, Ce, Lu, Yb and the Sc.

Embodiment two: present embodiment is a kind of preparation method of presoma of doping carbon nano material, specifically finishes according to the following steps: one, prepare raw material: according to chemical formula Mn _αCo _βNi _γM _y(OH) ₂By the Mn element: Co element: Ni element: M element mol ratio is that α: β: γ: y prepares soluble manganese salt, solubility cobalt salt, soluble nickel salt and soluble M salt; Two, preparation hybrid metal ion salt solution: soluble manganese salt, solubility cobalt salt, soluble nickel salt and soluble M salt that step 1 is prepared join in the solvent and mix, and being configured to the hybrid metal ion concentration is the hybrid metal ion salt solution of 0.01mol/L ~ 5mol/L; Three, preparation precipitation reagent: solubility hydroxide is added in the solvent, be configured to OH ^-Concentration is 0.1mol/L ~ 10mol/L precipitation reagent; Four, preparation complexing agent: solubility ammonium salt or ammoniacal liquor are added in the solvent, be configured to NH ₄ ⁺Concentration is 0.1mol/L ~ 10mol/L complexing agent; Five, preparation carbon nanomaterial suspension: carbon nanomaterial is scattered in the solvent, and being configured to carbon nanomaterial concentration is the carbon nanomaterial suspension of 0.1mg/L ~ 50g/L; Six, coprecipitation reaction: the hybrid metal ion concentration that step 2 is prepared is the hybrid metal ion salt solution of 0.01mol/L ~ 5mol/L, the OH of step 3 preparation ^-Concentration is the NH of 0.1mol/L ~ 10mol/L precipitation reagent, step 4 preparation ₄ ⁺Concentration is that the carbon nanomaterial concentration of 0.1mol/L ~ 10mol/L complexing agent and step 5 preparation is that the carbon nanomaterial suspension of 0.1mg/L ~ 50g/L adds in the reactor that the reaction initial soln is housed simultaneously, the hybrid metal ion concentration of step 2 preparation is that the adding speed of the hybrid metal ion salt solution of 0.01mol/L ~ 5mol/L is 0.1mL/min ~ 1000mL/min, the OH of step 3 preparation ^-Concentration is that the adding speed of 0.1mol/L ~ 10mol/L precipitation reagent is 0.1mL/min ~ 1000mL/min, the NH of step 4 preparation ₄ ⁺Concentration is that the adding speed of 0.1mol/L ~ 10mol/L complexing agent is 0.1mL/min ~ 1000mL/min, the carbon nanomaterial concentration of step 5 preparation is that the adding speed of the carbon nanomaterial suspension of 0.1mg/L ~ 50g/L is 0.1mL/min ~ 500mL/min, and temperature be 20 ℃ ~ 90 ℃, mixing speed be 100rpm～10000rpm, pH be 5 ~ 13 and inert gas shielding under react, namely obtain the spherical precipitation thing; Seven, washing is dry processes: the spherical precipitation thing that at first adopts the washed with de-ionized water step 6 to obtain, clean be neutrality to the pH of filtrate till, then be 20 ℃ ~ 150 ℃ in temperature and be dried to constant weight, namely obtain the Uniform Doped carbon nanomaterial, molecular formula is Mn _αCo _βNi _γM _y(OH) ₂Metal hydroxides.

Described Mn described in the present embodiment step 1 _αCo _βNi _γM _y(OH) ₂In 0＜α≤1,0≤β≤1,0≤γ≤1,0≤y≤0.5, and alpha+beta+γ+y=1, β+γ＞0, wherein said Mn _αCo _βNi _γM _y(OH) ₂Middle M is a kind of or wherein several among Cr, Al, Fe, Mg, Ag, Ti, Cu, V, Y, La, Tm, Gd, Ho, Ce, Lu, Yb and the Sc.

The volume of the reaction initial soln described in the present embodiment step 6 and the volumetric ratio of reactor are (0.001 ~ 0.8): 1.

When the described M of present embodiment is complex element, be mixed by any ratio between each element.

The complexing agent that the present embodiment step 4 obtains is except directly adding the reactor China and foreign countries that the reaction initial soln is housed, also can mix with the hybrid metal ion salt solution of step 2 preparation or the precipitation reagent of step 3 preparation in advance, carry out again the operation of step 6, take speed as 0.1mL/min ~ 1000mL/min adds in the reactor that the reaction initial soln is housed.Namely two kinds of materials that chemical reaction does not occur can be mixed in advance, carry out again the operation of step 6, take speed as 0.1mL/min ~ 1000mL/min adds in the reactor that the reaction initial soln is housed.

Except the carbon nanomaterial described in the present embodiment step 5 is scattered in the solvent, being configured to carbon nanomaterial concentration is outside the carbon nanomaterial suspension of 0.1mg/L ~ 50g/L, carbon nanomaterial can also be scattered in the hybrid metal ion salt solution of step 2 preparation, a kind of or wherein several in the complexing agent of the precipitation reagent of step 3 preparation and step 4 preparation, carbon nanomaterial concentration is 0.1mg/L ~ 50g/L in the suspension that obtains after the dispersion, namely shift to an earlier date the hybrid metal ion salt solution of carbon nanomaterial and step 2 preparation, a kind of in the complexing agent of the precipitation reagent of step 3 preparation and step 4 preparation or several mixing wherein, and then carry out the operation of step 6, take speed as 0.1mL/min ~ 1000mL/min adds in the reactor that the reaction initial soln is housed; Can also first carbon nanomaterial be scattered in the reaction initial soln in the reactor, carbon nanomaterial concentration is 0.1mg/L ~ 50g/L in the carbon nanomaterial that obtains after the dispersion/reaction initial soln suspension, and then carry out the operation of step 6, take speed as 0.1mL/min ~ 1000mL/min adds and to be equipped with in the reactor of carbon nanomaterial/reaction initial soln suspension; Namely can mix in advance two kinds of chemical reaction or two or more material do not occur, carry out again the operation of step 6, take speed as 0.1mL/min ~ 1000mL/min adds in the reactor that the reaction initial soln is housed.

Embodiment three: the difference of present embodiment and embodiment two is: the soluble manganese salt described in the step 2 is a kind of in manganese sulfate, manganese nitrate, manganese chloride, manganese sulfate hydrate, manganese nitrate hydrate and the manganese chloride hydrate or several mixture wherein.Other are identical with embodiment two.

When the described soluble manganese salt of present embodiment is mixture, be mixed by any ratio between each component.

Embodiment four: present embodiment and one of embodiment two or three difference are: the solubility cobalt salt described in the step 2 is a kind of in cobaltous sulfate, cobalt nitrate, cobalt chloride, cobaltous sulfate hydrate, cobalt nitrate hydrate and the cobalt chloride hydrate or several mixture wherein.Other are identical with embodiment two or three.

When the described solubility cobalt salt of present embodiment is mixture, be mixed by any ratio between each component.

Embodiment five: one of present embodiment and embodiment two to four difference is: the soluble nickel salt described in the step 2 is a kind of in nickelous sulfate, nickel nitrate, nickel chloride, nickelous sulfate hydrate, nickel nitrate hydrate and the nickel chloride hydrate or several mixture wherein.Other are identical with embodiment two to four.

When the described soluble nickel salt of present embodiment is mixture, be mixed by any ratio between each component.

Embodiment six: one of present embodiment and embodiment two to five difference is: the soluble M salt described in the step 2 is a kind of in sulfuric acid M, nitric acid M, chlorination M, sulfuric acid M hydrate, nitric acid M hydrate and the chlorination M hydrate or several mixture wherein.Other are identical with embodiment two to five.

When the described soluble M salt of present embodiment is mixture, be mixed by any ratio between each component.

Embodiment seven: one of present embodiment and embodiment two to six difference is: the solvent described in the step 2 is deionized water, methanol aqueous solution, ethanol water, aqueous acetone solution, the methanol/ethanol aqueous solution, the methanol/acetone aqueous solution, the ethanol/acetone aqueous solution or methanol/ethanol/aqueous acetone solution.Other are identical with embodiment two to six.

The described methanol aqueous solution of present embodiment is mixed by any ratio by methyl alcohol and deionized water and forms.

The described ethanol water of present embodiment is mixed by any ratio by ethanol and deionized water and forms.

The described aqueous acetone solution of present embodiment is mixed by any ratio by acetone and deionized water and forms.

The described methanol/ethanol aqueous solution of present embodiment is mixed by any ratio by methyl alcohol, ethanol and deionized water and forms.

The described methanol/acetone aqueous solution of present embodiment is mixed by any ratio by methyl alcohol, acetone and deionized water and forms.

The described ethanol/acetone aqueous solution of present embodiment is mixed by any ratio by ethanol, acetone and deionized water and forms.

Described methanol/ethanol/the aqueous acetone solution of present embodiment is mixed by any ratio by methyl alcohol, ethanol, acetone and deionized water and forms.

Embodiment eight: one of present embodiment and embodiment two to seven difference is: the solvent described in the step 3 is deionized water, methanol aqueous solution, ethanol water, aqueous acetone solution, the methanol/ethanol aqueous solution, the methanol/acetone aqueous solution, the ethanol/acetone aqueous solution or methanol/ethanol/aqueous acetone solution.Other are identical with embodiment two to seven.

Embodiment nine: one of present embodiment and embodiment two to eight difference is: the solubility hydroxide described in the step 3 is a kind of in NaOH, potassium hydroxide, lithium hydroxide and the barium hydroxide or several mixture wherein.Other are identical with embodiment two to eight.

When the described solubility hydroxide of present embodiment is mixture, be mixed by any ratio between each component.

Embodiment ten: one of present embodiment and embodiment two to nine difference is: the solubility ammonium salt described in the step 4 is a kind of in carbonic hydroammonium, ammonium carbonate, ammonium sulfate, ammonium hydrogen sulfate, ammonium chloride, ammonium phosphate, ammonium hydrogen phosphate and the ammonium dihydrogen phosphate or several mixture wherein.Other are identical with embodiment two to nine.

When the described solubility ammonium salt of present embodiment is mixture, be mixed by any ratio between each component.

Embodiment 11: one of present embodiment and embodiment two to ten difference is: the solvent described in the step 4 is deionized water, methanol aqueous solution, ethanol water, aqueous acetone solution, the methanol/ethanol aqueous solution, the methanol/acetone aqueous solution, the ethanol/acetone aqueous solution or methanol/ethanol/aqueous acetone solution.Other are identical with embodiment two to ten.

Embodiment 12: one of present embodiment and embodiment two to 11 difference is: the solvent described in the step 5 is deionized water, methanol aqueous solution, ethanol water, aqueous acetone solution, the methanol/ethanol aqueous solution, the methanol/acetone aqueous solution, the ethanol/acetone aqueous solution or methanol/ethanol/aqueous acetone solution.Other are identical with embodiment two to 11.

Embodiment 13: one of present embodiment and embodiment two to 12 difference is: the carbon nanomaterial described in the step 5 is a kind of in carbon nano-tube, Graphene, graphene oxide, intercalated graphite alkene, carbon nano-fiber and the Nano carbon balls or several mixture wherein.Other are identical with embodiment two to 12.

When the described carbon nanomaterial of present embodiment is mixture, be mixed by any ratio between each component.

Embodiment 14: one of present embodiment and embodiment two to 13 difference is: the reaction initial soln described in the step 6 is to be configured to NH in solvent or employing solubility ammonium salt or the ammoniacal liquor adding solvent ₄ ⁺Concentration is the ammonia solution of 0.01mol/L ~ 2mol/L, and wherein said solvent is deionized water, methanol aqueous solution, ethanol water, aqueous acetone solution, the methanol/ethanol aqueous solution, the methanol/acetone aqueous solution, the ethanol/acetone aqueous solution or methanol/ethanol/aqueous acetone solution; Wherein said solubility ammonium salt is a kind of in carbonic hydroammonium, ammonium carbonate, ammonium sulfate, ammonium hydrogen sulfate, ammonium chloride, ammonium phosphate, ammonium hydrogen phosphate and the ammonium dihydrogen phosphate or several mixture wherein.Other are identical with embodiment two to 13.

Embodiment 15: one of present embodiment and embodiment two to 14 difference is: the inert gas described in the step 6 is argon gas, nitrogen or argon gas/nitrogen mixture body.Other are identical with embodiment two to 14.

The described argon gas of present embodiment/nitrogen mixture body is mixed by the arbitrary volume ratio by argon gas and nitrogen.

Embodiment 16: present embodiment is a kind of preparation method of presoma of doping carbon nano material, specifically finishes according to the following steps: one, prepare raw material: according to chemical formula Mn _αCo _βNi _γM _yCO ₃By the Mn element: Co element: Ni element: M element mol ratio is that α: β: γ: y prepares soluble manganese salt, solubility cobalt salt, soluble nickel salt and soluble M salt; Two, preparation hybrid metal ion salt solution: soluble manganese salt, solubility cobalt salt, soluble nickel salt and soluble M salt that step 1 is prepared join in the solvent and mix, and being configured to the hybrid metal ion concentration is the hybrid metal ion salt solution of 0.01mol/L ~ 5mol/L; Three, preparation precipitation reagent: solubility hydroxide is added in the solvent, be configured to CO ₃ ^2-Concentration is 0.1mol/L ~ 10mol/L precipitation reagent; Four, preparation complexing agent: solubility ammonium salt or ammoniacal liquor are added in the solvent, be configured to NH ₄ ⁺Concentration is 0.1mol/L ~ 10mol/L complexing agent; Five, preparation carbon nanomaterial suspension: carbon nanomaterial is scattered in the solvent, and being configured to carbon nanomaterial concentration is the carbon nanomaterial suspension of 0.1mg/L ~ 50g/L; Six, coprecipitation reaction: the hybrid metal ion concentration that step 2 is prepared is the hybrid metal ion salt solution of 0.01mol/L ~ 5mol/L, the CO of step 3 preparation ₃ ^2-Concentration is the NH of 0.1mol/L ~ 10mol/L precipitation reagent, step 4 preparation ₄ ⁺Concentration is that the carbon nanomaterial concentration of 0.1mol/L ~ 10mol/L complexing agent and step 5 preparation is that the carbon nanomaterial suspension of 0.1mg/L ~ 50g/L adds in the reactor that the reaction initial soln is housed simultaneously, the hybrid metal ion concentration of step 2 preparation is that the adding speed of the hybrid metal ion salt solution of 0.01mol/L ~ 5mol/L is 0.1mL/min ~ 1000mL/min, the CO of step 3 preparation ₃ ^2-Concentration is that the adding speed of 0.1mol/L ~ 10mol/L precipitation reagent is 0.1mL/min ~ 1000mL/min, the NH of step 4 preparation ₄ ⁺Concentration is that the adding speed of 0.1mol/L ~ 10mol/L complexing agent is 0.1mL/min ~ 1000mL/min, the carbon nanomaterial concentration of step 5 preparation is that the adding speed of the carbon nanomaterial suspension of 0.1mg/L ~ 50g/L is 0.1mL/min ~ 500mL/min, and temperature be 20 ℃ ~ 90 ℃, mixing speed be 100rpm ~ 10000rpm, pH be 5 ~ 13 and inert gas shielding under react, namely obtain the spherical precipitation thing; Seven, washing is dry processes: the spherical precipitation thing that at first adopts the washed with de-ionized water step 6 to obtain, clean be neutrality to the pH of filtrate till, then be 20 ℃ ~ 150 ℃ in temperature and be dried to constant weight, namely obtain the Uniform Doped carbon nanomaterial, molecular formula is Mn _αCo _βNi _γM _yCO ₃Metal carbonate.

Described Mn described in the present embodiment step 1 _αCo _βNi _γM _yCO ₃In 0＜α≤1,0≤β≤1,0≤γ≤1,0≤y≤0.5, and alpha+beta+γ+y=1, β+γ＞0, wherein said Mn _αCo _βNi _γM _yCO ₃Middle M is a kind of or wherein several among Cr, Al, Fe, Mg, Ag, Ti, Cu, V, Y, La, Tm, Gd, Ho, Ce, Lu, Yb and the Sc.

Embodiment 17: the difference of present embodiment and embodiment 16 is: the soluble manganese salt described in the step 2 is a kind of in manganese sulfate, manganese nitrate, manganese chloride, manganese sulfate hydrate, manganese nitrate hydrate and the manganese chloride hydrate or several mixture wherein.Other are identical with embodiment 16.

Embodiment 18: present embodiment and one of embodiment 16 or 17 difference are: the solubility cobalt salt described in the step 2 is a kind of in cobaltous sulfate, cobalt nitrate, cobalt chloride, cobaltous sulfate hydrate, cobalt nitrate hydrate and the cobalt chloride hydrate or several mixture wherein.Other are identical with embodiment 16 or 17.

Embodiment 19: one of present embodiment and embodiment 16 to 18 difference is: the soluble nickel salt described in the step 2 is a kind of in nickelous sulfate, nickel nitrate, nickel chloride, nickelous sulfate hydrate, nickel nitrate hydrate and the nickel chloride hydrate or several mixture wherein.Other are identical with embodiment 16 to 18.

Embodiment 20: one of present embodiment and embodiment 16 to 19 difference is: the soluble M salt described in the step 2 is a kind of in sulfuric acid M, nitric acid M, chlorination M, sulfuric acid M hydrate, nitric acid M hydrate and the chlorination M hydrate or several mixture wherein.Other are identical with embodiment 16 to 19.

Embodiment 21: one of present embodiment and embodiment 16 to 20 difference is: the solvent described in the step 2 is deionized water, methanol aqueous solution, ethanol water, aqueous acetone solution, the methanol/ethanol aqueous solution, the methanol/acetone aqueous solution, the ethanol/acetone aqueous solution or methanol/ethanol/aqueous acetone solution.Other are identical with embodiment 16 to 20.

Embodiment 22: one of present embodiment and embodiment 16 to 21 difference is: the solvent described in the step 3 is deionized water, methanol aqueous solution, ethanol water, aqueous acetone solution, the methanol/ethanol aqueous solution, the methanol/acetone aqueous solution, the ethanol/acetone aqueous solution or methanol/ethanol/aqueous acetone solution.Other are identical with embodiment 16 to 21.

Embodiment 23: one of present embodiment and embodiment 16 to 22 difference is: the soluble carbonate salt described in the step 3 is a kind of in sodium carbonate, sodium acid carbonate, potash, ammonium carbonate and the carbonic hydroammonium or several mixture wherein.Other are identical with embodiment 16 to 22.

When the described soluble carbonate salt of present embodiment is mixture, be mixed by any ratio between each component.

Embodiment 24: one of present embodiment and embodiment 16 to 23 difference is: the solubility ammonium salt described in the step 4 is a kind of in carbonic hydroammonium, ammonium carbonate, ammonium sulfate, ammonium hydrogen sulfate, ammonium chloride, ammonium phosphate, ammonium hydrogen phosphate and the ammonium dihydrogen phosphate or several mixture wherein.Other are identical with embodiment 16 to 23.

Embodiment 25: one of present embodiment and embodiment 16 to 24 difference is: the solvent described in the step 4 is deionized water, methanol aqueous solution, ethanol water, aqueous acetone solution, the methanol/ethanol aqueous solution, the methanol/acetone aqueous solution, the ethanol/acetone aqueous solution or methanol/ethanol/aqueous acetone solution.Other are identical with embodiment 16 to 24.

Embodiment 26: one of present embodiment and embodiment 16 to 25 difference is: the solvent described in the step 5 is deionized water, methanol aqueous solution, ethanol water, aqueous acetone solution, the methanol/ethanol aqueous solution, the methanol/acetone aqueous solution, the ethanol/acetone aqueous solution or methanol/ethanol/aqueous acetone solution.Other are identical with embodiment 16 to 25.

Embodiment 27: one of present embodiment and embodiment 16 to 26 difference is: the carbon nanomaterial described in the step 5 is a kind of in carbon nano-tube, Graphene, graphene oxide, intercalated graphite alkene, carbon nano-fiber and the Nano carbon balls or several mixture wherein.Other are identical with embodiment 16 to 26.

Embodiment 28: one of present embodiment and embodiment 16 to 27 difference is: the reaction initial soln described in the step 6 is to be configured to NH in solvent or employing solubility ammonium salt or the ammoniacal liquor adding solvent ₄ ⁺Concentration is the ammonia solution of 0.01mol/L ~ 2mol/L, and wherein said solvent is deionized water, methanol aqueous solution, ethanol water, aqueous acetone solution, the methanol/ethanol aqueous solution, the methanol/acetone aqueous solution, the ethanol/acetone aqueous solution or methanol/ethanol/aqueous acetone solution; Wherein said solubility ammonium salt is a kind of in carbonic hydroammonium, ammonium carbonate, ammonium sulfate, ammonium hydrogen sulfate, ammonium chloride, ammonium phosphate, ammonium hydrogen phosphate and the ammonium dihydrogen phosphate or several mixture wherein.Other are identical with embodiment 16 to 27.

Embodiment 29: one of present embodiment and embodiment 16 to 28 difference is: the inert gas described in the step 6 is argon gas, nitrogen or argon gas/nitrogen mixture body.Other are identical with embodiment 16 to 28.

Embodiment 30: present embodiment is a kind of spherical lithium metal oxide positive electrode, and spherical lithium metal oxide positive electrode is prepared from by the presoma of lithium-containing compound and embodiment one described doping carbon nano material.

The ratio of the amount of the Li elemental substance in the presoma of the described doping carbon nano material of present embodiment in the total amount of substance of metallic element and the described lithium-containing compound of present embodiment is 1:(1 ~ 1.42)

The presoma of the described doping carbon nano material of present embodiment is that Uniform Doped carbon nanomaterial, molecular formula are Mn _αCo _βNi _γM _y(OH) ₂Metal hydroxides or Uniform Doped carbon nanomaterial, molecular formula be Mn _αCo _βNi _γM _yCO ₃Metal carbonate; Wherein said Mn _αCo _βNi _γM _y(OH) ₂In 0＜α≤1,0≤β≤1,0≤γ≤1,0≤y≤0.5, and alpha+beta+γ+y=1, β+γ＞0, described Mn _αCo _βNi _γM _y(OH) ₂Middle M is a kind of or wherein several among Cr, Al, Fe, Mg, Ag, Ti, Cu, V, Y, La, Tm, Gd, Ho, Ce, Lu, Yb and the Sc; Wherein said Mn _αCo _βNi _γM _yCO ₃In 0＜α≤1,0≤β≤1,0≤γ≤1,0≤y≤0.5, and alpha+beta+γ+y=1, β+γ＞0, described Mn _αCo _βNi _γM _yCO ₃Middle M is a kind of or wherein several among Cr, Al, Fe, Mg, Ag, Ti, Cu, V, Y, La, Tm, Gd, Ho, Ce, Lu, Yb and the Sc.

Embodiment 31: the difference of embodiment and embodiment 30 is: described lithium-containing compound is a kind of in lithium hydroxide, lithium carbonate, lithium acetate, lithium oxalate, lithium nitrate and the lithium citrate or several mixture wherein.Other are identical with embodiment 30.

When the described lithium-containing compound of present embodiment is mixture, be mixed by any ratio between each component.

Embodiment 32: present embodiment is a kind of preparation method of spherical lithium metal oxide positive electrode, specifically finish according to the following steps: one, presoma preliminary treatment: the presoma of embodiment one described doping carbon nano material at 200 ℃ ~ 800 ℃ pre-burning 1h ~ 12h, is obtained presoma after the preliminary treatment; Two, mixed lithium sintering: presoma after the preliminary treatment is mixed with lithium-containing compound, is 600 ℃ ~ 1200 ℃ roasting 3h ~ 36h in temperature then, cools to room temperature with the furnace and namely obtains spherical lithium metal oxide positive electrode.

The presoma of the doping carbon nano material described in the present embodiment step 1 is that Uniform Doped carbon nanomaterial, molecular formula are Mn _αCo _βNi _γM _y(OH) ₂Metal hydroxides or Uniform Doped carbon nanomaterial, molecular formula be Mn _αCo _βNi _γM _yCO ₃Metal carbonate; Wherein said Mn _αCo _βNi _γM _y(OH) ₂In 0＜α≤1,0≤β≤1,0≤γ≤1,0≤y≤0.5, and alpha+beta+γ+y=1, β+γ＞0, described Mn _αCo _βNi _γM _y(OH) ₂Middle M is a kind of or wherein several among Cr, Al, Fe, Mg, Ag, Ti, Cu, V, Y, La, Tm, Gd, Ho, Ce, Lu, Yb and the Sc; Wherein said Mn _αCo _βNi _γM _yCO ₃In 0＜α≤1,0≤β≤1,0≤γ≤1,0≤y≤0.5, and alpha+beta+γ+y=1, β+γ＞0, described Mn _αCo _βNi _γM _yCO ₃Middle M is a kind of or wherein several among Cr, Al, Fe, Mg, Ag, Ti, Cu, V, Y, La, Tm, Gd, Ho, Ce, Lu, Yb and the Sc.

The ratio of the amount of the Li elemental substance in the presoma of the doping carbon nano material described in the present embodiment step 1 in the total amount of substance of metallic element and the lithium-containing compound described in the step 2 is 1:(1 ~ 1.42).

Can ignore the described presoma preliminary treatment of present embodiment, directly adopt the presoma of embodiment one described doping carbon nano material to mix with lithium-containing compound, then be 600 ℃ ~ 1200 ℃ roasting 3h ~ 36h in temperature, cool to room temperature with the furnace and namely obtain spherical lithium metal oxide positive electrode.When the presoma of embodiment one described doping carbon nano material is metal hydroxides, generally can ignore directly mixed lithium sintering of the described presoma preliminary treatment of present embodiment; When the presoma of embodiment one described doping carbon nano material is metal carbonate, need through the described presoma preliminary treatment of present embodiment, more mixed lithium sintering.

Embodiment 33: the difference of present embodiment and embodiment 32 is: a kind of in lithium-containing compound lithium hydroxide, lithium carbonate, lithium acetate, lithium oxalate, lithium nitrate and the lithium citrate described in the step 2 or several mixture wherein.Other are identical with embodiment 32.

Adopt following verification experimental verification effect of the present invention:

Test one: a kind of preparation method of presoma of doping carbon nano material, specifically finish: one, prepare raw material: according to chemical formula Mn according to the following steps _2/3Co _1/6Ni _1/6CO ₃By the Mn element: Co element: Ni element: M element mol ratio is that 4:1:1 prepares manganese sulfate, cobaltous sulfate and nickelous sulfate; Two, preparation hybrid metal ion salt solution: manganese sulfate, cobaltous sulfate and nickelous sulfate that step 1 is prepared join in the deionized water and mix, and being configured to the hybrid metal ion concentration is the hybrid metal ion salt solution of 1mol/L; Three, preparation precipitation reagent: sodium carbonate is added in the deionized water, be configured to CO ₃ ^2-Concentration is the 1mol/L precipitation reagent; Four, preparation complexing agent: ammoniacal liquor is added in the deionized water, be configured to NH ₄ ⁺Concentration is the 0.1mol/L complexing agent; Five, preparation carbon nanomaterial suspension: carbon nanomaterial is scattered in the deionized water, and being configured to carbon nanomaterial concentration is the carbon nanomaterial suspension of 1g/L; Six, coprecipitation reaction: the hybrid metal ion concentration that step 2 is prepared is the hybrid metal ion salt solution of 1mol/L, the CO of step 3 preparation ₃ ^2-Concentration is the NH of 1mol/L precipitation reagent, step 4 preparation ₄ ⁺Concentration is that the carbon nanomaterial concentration of 0.1mol/L complexing agent and step 5 preparation is that the carbon nanomaterial suspension of 1g/L adds in the reactor that the reaction initial soln is housed simultaneously, the hybrid metal ion concentration of step 2 preparation is that the adding speed of the hybrid metal ion salt solution of 1mol/L is 500mL/min, the CO of step 3 preparation ₃ ^2-Concentration is that the adding speed of 1mol/L precipitation reagent is 500mL/min, the NH of step 4 preparation ₄ ⁺Concentration is that the adding speed of 0.1mol/L complexing agent is 500mL/min, the carbon nanomaterial concentration of step 5 preparation is that the adding speed of the carbon nanomaterial suspension of 1g/L is 250mL/min, and temperature be 60 ℃, mixing speed be 1500rpm, pH be 7.5 and nitrogen protection under react, namely obtain the spherical precipitation thing; Seven, washing is dry processes: the spherical precipitation thing that at first adopts the washed with de-ionized water step 6 to obtain, clean be neutrality to the pH of filtrate till, then be 120 ℃ in temperature and be dried to constant weight, namely obtain the Uniform Doped carbon nanomaterial, molecular formula is Mn _2/3Co _1/6Ni _1/6CO ₃Metal carbonate.

Testing the reaction initial soln described in the step 6 is to be configured to NH in the ammoniacal liquor adding deionized water ₄ ⁺Concentration is the ammonia solution of 0.05mol/L.

Testing the volume of the reaction initial soln described in the step 6 and the volumetric ratio of reactor is 0.2:1.

Test a contrast test: one, prepare raw material: according to chemical formula Mn _2/3Co _1/6Ni _1/6CO ₃By the Mn element: Co element: Ni element: M element mol ratio is that 4:1:1 prepares manganese sulfate, cobaltous sulfate and nickelous sulfate; Two, preparation hybrid metal ion salt solution: manganese sulfate, cobaltous sulfate and nickelous sulfate that step 1 is prepared join in the deionized water and mix, and being configured to the hybrid metal ion concentration is the hybrid metal ion salt solution of 1mol/L; Three, preparation precipitation reagent: sodium carbonate is added in the deionized water, be configured to CO ₃ ^2-Concentration is the 1mol/L precipitation reagent; Four, preparation complexing agent: ammoniacal liquor is added in the deionized water, be configured to NH ₄ ⁺Concentration is the 0.1mol/L complexing agent; Five, coprecipitation reaction: the hybrid metal ion concentration that step 2 is prepared is the hybrid metal ion salt solution of 1mol/L, the CO of step 3 preparation ₃ ^2-Concentration is the NH of 1mol/L precipitation reagent and step 4 preparation ₄ ⁺Concentration is that the 0.1mol/L complexing agent adds in the reactor that the reaction initial soln is housed simultaneously, and the hybrid metal ion concentration of step 2 preparation is that the adding speed of the hybrid metal ion salt solution of 1mol/L is 500mL/min, the CO of step 3 preparation ₃ ^2-Concentration is that the adding speed of 1mol/L precipitation reagent is 500mL/min, the NH of step 4 preparation ₄ ⁺Concentration is that the adding speed of 0.1mol/L complexing agent is 500mL/min, and temperature be 60 ℃, mixing speed be 1500rpm, pH be 7.5 and nitrogen protection under react, namely obtain the spherical precipitation thing; Six, washing is dry processes: the spherical precipitation thing that at first adopts the washed with de-ionized water step 5 to obtain, clean be neutrality to the pH of filtrate till, then be 120 ℃ in temperature and be dried to constant weight, namely obtaining molecular formula is Mn _2/3Co _1/6Ni _1/6CO ₃Metal carbonate.

Testing the volume of the reaction initial soln described in the contrast test step 5 and the volumetric ratio of reactor is 0.2:1.

(Uniform Doped carbon nanomaterial, molecular formula are Mn to adopt X-ray diffractometer to detect the presoma of testing a doping carbon nano material for preparing _2/3Co _1/6Ni _1/6CO ₃Metal carbonate), testing result as shown in Figure 1, Fig. 1 is the spherical lithium metal oxide positive electrode XRD figure of test one preparation, the material crystalline structure that is synthesized as seen in Figure 1 is complete, without other impurity.

(Uniform Doped carbon nanomaterial, molecular formula are Mn to the presoma of the doping carbon nano material of employing scanning electron microscopy test one preparation _2/3Co _1/6Ni _1/6CO ₃Metal carbonate), testing result as shown in Figure 2, Fig. 2 is that (amplifies 10000 times SEM figure, the presoma sphericity that can observe the doping carbon nano material that test one prepares by Fig. 2 is higher for the presoma of the doping carbon nano material of test one preparation.

Test two: a kind of preparation method of spherical lithium metal oxide positive electrode, specifically finish according to the following steps: one, presoma preliminary treatment: will test the presoma of a doping carbon nano material that obtains at 500 ℃ of pre-burning 12h, and obtain presoma after the preliminary treatment; Two, mixed lithium sintering: presoma mixes with lithium hydroxide after the preliminary treatment that step 1 is obtained, and is 900 ℃ of roasting 30h in temperature then, cools to room temperature with the furnace and namely obtains spherical lithium metal oxide positive electrode.

The ratio of testing described in two step 1 amount of the Li elemental substance in the total amount of substance of metallic element and the lithium hydroxide described in the step 2 in the presoma of the test one doping carbon nano material that obtains is 1:1.25.

Test two contrast tests: one, presoma preliminary treatment: will test the molecular formula that a contrast test obtains is Mn _2/3Co _1/6Ni _1/6CO ₃Metal carbonate at 500 ℃ of pre-burning 12h, obtain presoma after the preliminary treatment; Two, mixed lithium sintering: presoma mixes with lithium hydroxide after the preliminary treatment that step 1 is obtained, and is 900 ℃ of roasting 30h in temperature then, cools to room temperature with the furnace and namely obtains spherical lithium metal oxide positive electrode.

Adopt X-ray diffractometer to detect the spherical lithium metal oxide positive electrode of test two preparations, testing result as shown in Figure 3, Fig. 3 is the spherical lithium metal oxide positive electrode XRD figure of test two preparations, the spherical lithium metal oxide positive electrode crystalline structures that can find out test two preparations by XRD data among Fig. 3 are complete, thereby and can observe significantly the distinctive superlattice ordered structure of rich lithium material fingerprint peaks in 20 ~ 25 degree scope intervals and proved and adopt the method to synthesize crystalline structure rich lithium material complete, free from foreign meter.

Adopt the spherical lithium metal oxide positive electrode of scanning electron microscopy test two preparations, testing result as shown in Figure 4, Fig. 4 is that the spherical lithium metal oxide positive electrode of test two preparations amplifies 5000 times SEM figure, and the spherical lithium metal oxide anode material spherical degree that can observe from Fig. 4 by testing two preparations is higher.

Adopting the performance test of new prestige high accuracy battery is the spherical lithium metal oxide positive electrode of testing experiment two preparations and the spherical lithium metal oxide positive electrode of test two contrast tests preparation, what use during test is that model is the CR2025 button cell, the employing metal lithium sheet is negative pole, electrolyte is that the volume ratio that contains 1mol/L-1LiPF6 is the EC+DEC+DMC mixed system of 1:1:1, uses microporous polypropylene membrane as barrier film.The electrode plates for preparing moisture and oxygen content under argon gas atmosphere are lower than in the glove box of 5ppm, are assembled into Li/ active material half-cell, battery carries out charge-discharge test with the 0.1C multiplying power, and discharging and recharging the interval is 2.0 ~ 4.6V.Testing result as shown in Figure 5, Fig. 5 is charging and discharging curve figure, A represents to test the spherical lithium metal oxide positive electrode charge graph of two preparations among the figure, B represents to test the spherical lithium metal oxide anode material discharging curve chart of two preparations among the figure, C represents to test the spherical lithium metal oxide positive electrode charge graph of two contrast tests preparation among the figure, D represents to test the spherical lithium metal oxide anode material discharging curve chart of two contrast tests preparation among the figure, the spherical lithium metal oxide positive electrode initial charge specific capacity that can observe the preparation of test two contrast tests by Fig. 5 is 324mAh/g, specific discharge capacity is 255mAh/g, and enclosed pasture efficient is 78% first; The spherical lithium metal oxide positive electrode initial charge specific capacity of test two preparations is 335mAh/g, specific discharge capacity is 303mAh/g, enclosed pasture efficient is 90% first, and the spherical lithium metal oxide positive electrodes of therefore testing as can be known two preparations compare first with the spherical lithium metal oxide positive electrode of test two contrast tests preparation that enclosed pasture efficient has had lifting by a relatively large margin.

Adopting the performance test of new prestige high accuracy battery is the spherical lithium metal oxide positive electrode of testing experiment two preparations and the spherical lithium metal oxide positive electrode of test two contrast tests preparation, what use during test is that model is the CR2025 button cell, the employing metal lithium sheet is negative pole, electrolyte is that the volume ratio that contains 1mol/L-1LiPF6 is the EC+DEC+DMC mixed system of 1:1:1, uses microporous polypropylene membrane as barrier film.The electrode plates for preparing moisture and oxygen content under argon gas atmosphere are lower than in the glove box of 5ppm, are assembled into Li/ active material half-cell, battery carries out charge-discharge test with the 1C multiplying power, and discharging and recharging the interval is 2.0 ~ 4.6V.Testing result as shown in Figure 6, Fig. 6 is the high rate performance curve chart, A represents to test the high rate performance curve chart of the two spherical lithium metal oxide positive electrodes that prepare among the figure, B represents to test the high rate performance curve chart of the spherical lithium metal oxide positive electrode of two contrast tests preparation among the figure, and the spherical lithium metal oxide positive electrode 1C discharge capacity that can observe the preparation of test two contrast tests by Fig. 6 is 185mAh/g; The spherical lithium metal oxide positive electrode 1C discharge capacity that test two prepares is 218mAh/g, therefore tests as can be known the spherical lithium metal oxide positive electrodes of two preparations and compares high rate performance lifting 18% with the spherical lithium metal oxide positive electrode of test two contrast tests preparation.

Adopt the new JZ-7 type tap density instrument of essence to come the tap density of sample powder is carried out spherical lithium metal oxide positive electrode, commercialization cobalt acid lithium and the commercialization ternary material of determination test two preparations according to the requirement of GB GB/T 5162-2006/ISO3953:1993, testing result is as shown in table 1, Data Comparison by table 1 as can be known, the spherical lithium metal oxide positive electrode tap density of testing as can be seen from Table 1 two preparations is better than the commercialization ternary material, has substantially reached the tap density level of commercialization cobalt acid lithium.

Table 1

Sample	Tap density (g/cm ³)
		Commercialization cobalt acid lithium	2.3~2.6
The commercialization ternary material	2~2.2
		The spherical lithium metal oxide positive electrode of test two preparations	2.35

Test three: a kind of preparation method of presoma of doping carbon nano material, specifically finish: one, prepare raw material: according to chemical formula Mn according to the following steps _0.795Co _0.1Ni _0.1M _0.005(OH) ₂By the Mn element: Co element: Ni element: M element mol ratio is that 7.95:1:1:0.05 prepares nickel nitrate, cobalt nitrate, manganese nitrate and aluminum nitrate; Two, preparation hybrid metal ion salt solution: nickel nitrate, cobalt nitrate, manganese nitrate and aluminum nitrate that step 1 is prepared join in the deionized water and mix, and being configured to the hybrid metal ion concentration is the hybrid metal ion salt solution of 2mol/L; Three, preparation precipitation reagent: NaOH is added in the deionized water, be configured to OH ^-Concentration is the 2mol/L precipitation reagent; Four, preparation complexing agent: solubility ammonium salt or ammoniacal liquor are added in the deionized water, be configured to NH ₄ ⁺Concentration is the 0.15mol/L complexing agent; Five, preparation carbon nanomaterial suspension: carbon nanomaterial is scattered in the deionized water, and being configured to carbon nanomaterial concentration is the carbon nanomaterial suspension of 1.5g/L; Six, coprecipitation reaction: the hybrid metal ion concentration that step 2 is prepared is the hybrid metal ion salt solution of 2mol/L, the OH of step 3 preparation ^-Concentration is the NH of 2mol/L precipitation reagent, step 4 preparation ₄ ⁺Concentration is that the carbon nanomaterial concentration of 0.15mol/L complexing agent and step 5 preparation is that the carbon nanomaterial suspension of 1.5g/L adds in the reactor that the reaction initial soln is housed simultaneously, the hybrid metal ion concentration of step 2 preparation is that the adding speed of the hybrid metal ion salt solution of 2mol/L is 500mL/min, the OH of step 3 preparation ^-Concentration is that the adding speed of 2mol/L precipitation reagent is 500mL/min, the NH of step 4 preparation ₄ ⁺Concentration is that the adding speed of 0.15mol/L complexing agent is 500mL/min, the carbon nanomaterial concentration of step 5 preparation is that the adding speed of the carbon nanomaterial suspension of 1.5g/L is 250mL/min, and temperature be 60 ℃, mixing speed be 1200rpm, pH be 10.5 and inert gas shielding under react, namely obtain the spherical precipitation thing; Seven, washing is dry processes: the spherical precipitation thing that at first adopts the washed with de-ionized water step 6 to obtain, clean be neutrality to the pH of filtrate till, then be 120 ℃ in temperature and be dried to constant weight, namely obtain the Uniform Doped carbon nanomaterial, molecular formula is Mn _0.795Co _0.1Ni _0.1M _0.005(OH) ₂Metal hydroxides.

Testing the reaction initial soln described in three step 6 is to be configured to NH in the ammoniacal liquor adding deionized water ₄ ⁺Concentration is the ammonia solution of 0.1mol/L.

Testing the volume of the reaction initial soln described in three step 6 and the volumetric ratio of reactor is 0.75:1.

(Uniform Doped nano-carbon material, molecular formula are Mn to the presoma of the doping carbon nano materials of employing scanning electron microscopy test three preparations _0.795Co _0.1Ni _0.1M _0.005(OH) ₂Metal hydroxides), testing result as shown in Figure 7, Fig. 7 is that the presoma of doping carbon nano material amplifies 10000 times SEM figure, can observe by testing three by Fig. 7 and adopt doped carbon nanometer pipe precursor sphericities higher.

Test four: a kind of preparation method of spherical lithium metal oxide positive electrode, specifically finish according to the following steps: the presoma that will test the three doping carbon nano materials that obtain mixes with lithium hydroxide, then be 800 ℃ of roasting 30h in temperature, cool to room temperature with the furnace and namely obtain spherical lithium metal oxide positive electrode.

The ratio of the amount of the Li elemental substance in the presoma of the three doping carbon nano materials that obtain of test described in this test procedure one in the total amount of substance of metallic element and the lithium hydroxide is 1:1.05.

Adopt X-ray diffractometer to detect the spherical lithium metal oxide positive electrode of this test preparation, testing result as shown in Figure 8, Fig. 8 is the spherical lithium metal oxide positive electrode XRD figure of test four preparations, can find out that by XRD data among Fig. 8 the material crystalline structure that is synthesized is complete, without other impurity.

Adopt the spherical lithium metal oxide positive electrode of scanning electron microscopy test four preparations, testing result as shown in Figure 9, Fig. 9 is that the spherical lithium metal oxide positive electrode of test four preparations amplifies 5000 times SEM figure, and the spherical lithium metal oxide anode material spherical degree that can observe from Fig. 9 by testing four preparations is higher.

Adopt the new JZ-7 type tap density instrument of essence to come the tap density of sample powder is carried out spherical lithium metal oxide positive electrode, commercialization cobalt acid lithium and the commercialization ternary material of determination test four preparations according to the requirement of GB GB/T 5162-2006/ISO3953:1993, testing result is as shown in table 2, the spherical lithium metal oxide positive electrode tap density of testing as can be seen from Table 2 as can be known four preparations by the Data Comparison of table 2 is better than the commercialization ternary material, has substantially reached the tap density level of commercialization cobalt acid lithium.

Table 2

Sample	Tap density (g/cm ³_
		Commercialization cobalt acid lithium	2.3~2.6
The commercialization ternary material	2~2.2
		The spherical lithium metal oxide positive electrode of test four preparations	2.4

Test five: a kind of preparation method of presoma of doping carbon nano material, specifically finish: one, prepare raw material: according to chemical formula Mn according to the following steps _2/3Co _1/6Ni _1/6CO ₃By the Mn element: Co element: Ni element: M element mol ratio is that 4:1:1 prepares manganese sulfate, cobaltous sulfate and nickelous sulfate; Two, preparation hybrid metal ion salt solution: manganese sulfate, cobaltous sulfate and nickelous sulfate that step 1 is prepared join in the deionized water and mix, and being configured to the hybrid metal ion concentration is the hybrid metal ion salt solution of 1mol/L; Three, preparation precipitation reagent: sodium carbonate is added in the deionized water, be configured to CO ₃ ^2-Concentration is the 1mol/L precipitation reagent; Four, preparation complexing agent: ammoniacal liquor is added in the deionized water, be configured to NH ₄ ⁺Concentration is the 0.1mol/L complexing agent; Five, preparation carbon nanomaterial suspension: carbon nanomaterial is scattered in the deionized water, and being configured to carbon nanomaterial concentration is the carbon nanomaterial suspension of 1g/L; Six, coprecipitation reaction: the hybrid metal ion concentration that step 2 is prepared is the hybrid metal ion salt solution of 1mol/L, the CO of step 3 preparation ₃ ^2-Concentration is the NH of 1mol/L precipitation reagent, step 4 preparation ₄ ⁺Concentration is that the carbon nanomaterial concentration of 0.1mol/L complexing agent and step 5 preparation is that the carbon nanomaterial suspension of 1g/L adds in the reactor that the reaction initial soln is housed simultaneously, the hybrid metal ion concentration of step 2 preparation is that the adding speed of the hybrid metal ion salt solution of 1mol/L is 500mL/min, the CO of step 3 preparation ₃ ^2-Concentration is that the adding speed of 1mol/L precipitation reagent is 500mL/min, the NH of step 4 preparation ₄ ⁺Concentration is that the adding speed of 0.1mol/L complexing agent is 500mL/min, the carbon nanomaterial concentration of step 5 preparation is that the adding speed of the carbon nanomaterial suspension of 1g/L is 250mL/min, and temperature be 60 ℃, mixing speed be 1500rpm, pH be 7.5 and nitrogen protection under react, namely obtain the spherical precipitation thing; Seven, washing is dry processes: the spherical precipitation thing that at first adopts the washed with de-ionized water step 6 to obtain, clean be neutrality to the pH of filtrate till, then be 120 ℃ in temperature and be dried to constant weight, namely obtain the Uniform Doped carbon nanomaterial, molecular formula is Mn _2/3Co _1/6Ni _1/6CO ₃Metal carbonate.

Testing the reaction initial soln described in five step 6 is deionized water.

Testing the volume of the reaction initial soln described in five step 6 and the volumetric ratio of reactor is 0.5:1.。

Adopt the presoma of the doping carbon nano material of scanning electron microscopy test five preparations, testing result as shown in figure 10, Figure 10 is that the presoma of the doping carbon nano material of test five preparations amplifies 5000 times SEM figure, as shown in Figure 10, although adopting aqueous solvent also is the higher particle of sphericity as the precursor of reaction initial soln preparation, but it is more can not can be observed ball particle around the spheric granules, is unfavorable for the raising of tap density.

The preparation method of test six, a kind of spherical lithium metal oxide positive electrode, specifically finish according to the following steps: one, presoma preliminary treatment: will test the presoma of the five doping carbon nano materials that obtain at 500 ℃ of pre-burning 12h, and obtain presoma after the preliminary treatment; Two, mixed lithium sintering: presoma mixes with lithium hydroxide after the preliminary treatment that step 2 is obtained, and is 850 ℃ of roasting 30h in temperature then, cools to room temperature with the furnace and namely obtains spherical lithium metal oxide positive electrode.

The ratio of testing described in six step 1 amount of the Li elemental substance in the total amount of substance of metallic element and the lithium hydroxide described in the step 2 in the presoma of the test five doping carbon nano materials that obtain is 1:1.27.

Adopt the new JZ-7 type tap density instrument of essence to come the tap density of sample powder is carried out the spherical lithium metal oxide positive electrode of determination test six preparations according to the requirement of GB GB/T 5162-2006/ISO3953:1993, commercialization cobalt acid lithium and commercialization ternary material, testing result is as shown in table 3, the spherical lithium metal oxide positive electrode tap density of testing as can be known six preparations by the Data Comparison of table 3 is better than the commercialization ternary material, substantially reached the tap density level of commercialization cobalt acid lithium, but owing to not becoming ball particle slightly many in the material, its tap density is a little less than the spherical lithium metal oxide positive electrode of test two preparations.

Table 3

Sample	Tap density (g/cm ³)
		Commercialization cobalt acid lithium	2.3~2.6
The commercialization ternary material	2~2.2
		The anodal material of spherical lithium metal oxide of test six preparations	2.3

Test seven: a kind of preparation method of presoma of doping carbon nano material, specifically finish: one, prepare raw material: according to chemical formula Mn according to the following steps _1/3Co _1/3Ni _1/3CO ₃By the Mn element: Co element: Ni element: M element mol ratio is that 1:1:1 prepares manganese sulfate, cobaltous sulfate and nickelous sulfate; Two, preparation hybrid metal ion salt solution: manganese sulfate, cobaltous sulfate and nickelous sulfate that step 1 is prepared join in the deionized water and mix, and being configured to the hybrid metal ion concentration is the hybrid metal ion salt solution of 1mol/L; Three, preparation precipitation reagent: sodium carbonate is added in the deionized water, be configured to CO ₃ ^2-Concentration is the 1mol/L precipitation reagent; Four, preparation complexing agent: ammoniacal liquor is added in the deionized water, be configured to NH ₄ ⁺Concentration is the 0.1mol/L complexing agent; Five, preparation carbon nanomaterial suspension: carbon nanomaterial is scattered in the deionized water, and being configured to carbon nanomaterial concentration is the carbon nanomaterial suspension of 1g/L; Six, coprecipitation reaction: the hybrid metal ion concentration that step 2 is prepared is the hybrid metal ion salt solution of 1mol/L, the CO of step 3 preparation ₃ ^2-Concentration is the NH of 1mol/L precipitation reagent, step 4 preparation ₄ ⁺Concentration is that the carbon nanomaterial concentration of 0.1mol/L complexing agent and step 5 preparation is that the carbon nanomaterial suspension of 1g/L adds in the reactor that the reaction initial soln is housed simultaneously, the hybrid metal ion concentration of step 2 preparation is that the adding speed of the hybrid metal ion salt solution of 1mol/L is 500mL/min, the CO of step 3 preparation ₃ ^2-Concentration is that the adding speed of 1mol/L precipitation reagent is 500mL/min, the NH of step 4 preparation ₄ ⁺Concentration is that the adding speed of 0.1mol/L complexing agent is 500mL/min, the carbon nanomaterial concentration of step 5 preparation is that the adding speed of the carbon nanomaterial suspension of 1g/L is 250mL/min, and temperature be 60 ℃, mixing speed be 1500rpm, pH be 7.5 and nitrogen protection under react, namely obtain the spherical precipitation thing; Seven, washing is dry processes: the spherical precipitation thing that at first adopts the washed with de-ionized water step 6 to obtain, clean be neutrality to the pH of filtrate till, then be 120 ℃ in temperature and be dried to constant weight, namely obtain the Uniform Doped carbon nanomaterial, molecular formula is Mn _1/3Co _1/3Ni _1/3CO ₃Metal carbonate.

Testing the reaction initial soln described in seven step 6 is deionized water.

Testing the volume of the reaction initial soln described in seven step 6 and the volumetric ratio of reactor is 0.02:1.

Test eight: a kind of preparation method of spherical lithium metal oxide positive electrode, specifically finish according to the following steps: one, presoma preliminary treatment: will test the presoma of the seven doping carbon nano materials that obtain at 500 ℃ of pre-burning 12h, and obtain presoma after the preliminary treatment; Two, mixed lithium sintering: presoma mixes with lithium hydroxide after the preliminary treatment that step 2 is obtained, and is 800 ℃ of roasting 30h in temperature then, cools to room temperature with the furnace and namely obtains spherical lithium metal oxide positive electrode.

The ratio of testing described in eight step 1 amount of the Li elemental substance in the total amount of substance of metallic element and the lithium hydroxide described in the step 2 in the presoma of the test seven doping carbon nano materials that obtain is 1:1.

Claims

1. the presoma of a doping carbon nano material, the presoma that it is characterized in that the doping carbon nano material is that Uniform Doped carbon nanomaterial, molecular formula are Mn _αCo _βNi _γM _y(OH) ₂Metal hydroxides or Uniform Doped carbon nanomaterial, molecular formula be Mn _αCo _βNi _γM _yCO ₃Metal carbonate; Wherein said Mn _αCo _βNi _γM _y(OH) ₂In 0＜α≤1,0≤β≤1,0≤γ≤1,0≤y≤0.5, and alpha+beta+γ+y=1, β+γ＞0, described Mn _αCo _βNi _γM _y(OH) ₂Middle M is a kind of or wherein several among Cr, Al, Fe, Mg, Ag, Ti, Cu, V, Y, La, Tm, Gd, Ho, Ce, Lu, Yb and the Sc; Wherein said Mn _αCo _βNi _γM _yCO ₃In 0＜α≤1,0≤β≤1,0≤γ≤1,0≤y≤0.5, and alpha+beta+γ+y=1, β+γ＞0, described Mn _αCo _βNi _γM _yCO ₃Middle M is a kind of or wherein several among Cr, Al, Fe, Mg, Ag, Ti, Cu, V, Y, La, Tm, Gd, Ho, Ce, Lu, Yb and the Sc.

2. the preparation method of the presoma of a kind of doping carbon nano material as claimed in claim 1 is characterized in that the preparation method of the presoma of doping carbon nano material finishes according to the following steps: one, prepare raw material: according to chemical formula Mn _αCo _βNi _γM _y(OH) ₂By the Mn element: Co element: Ni element: M element mol ratio is that α: β: γ: y prepares soluble manganese salt, solubility cobalt salt, soluble nickel salt and soluble M salt; Two, preparation hybrid metal ion salt solution: soluble manganese salt, solubility cobalt salt, soluble nickel salt and soluble M salt that step 1 is prepared join in the solvent and mix, and being configured to the hybrid metal ion concentration is the hybrid metal ion salt solution of 0.01mol/L ~ 5mol/L; Three, preparation precipitation reagent: solubility hydroxide is added in the solvent, be configured to OH ^-Concentration is 0.1mol/L ~ 10mol/L precipitation reagent; Four, preparation complexing agent: solubility ammonium salt or ammoniacal liquor are added in the solvent, be configured to NH ₄ ⁺Concentration is 0.1mol/L ~ 10mol/L complexing agent; Five, preparation carbon nanomaterial suspension: carbon nanomaterial is scattered in the solvent, and being configured to carbon nanomaterial concentration is the carbon nanomaterial suspension of 0.1mg/L ~ 50g/L; Six, coprecipitation reaction: the hybrid metal ion concentration that step 2 is prepared is the hybrid metal ion salt solution of 0.01mol/L ~ 5mol/L, the OH of step 3 preparation ^-Concentration is the NH of 0.1mol/L ~ 10mol/L precipitation reagent, step 4 preparation ₄ ⁺Concentration is that the carbon nanomaterial concentration of 0.1mol/L ~ 10mol/L complexing agent and step 5 preparation is that the carbon nanomaterial suspension of 0.1mg/L ~ 50g/L adds in the reactor that the reaction initial soln is housed simultaneously, the hybrid metal ion concentration of step 2 preparation is that the adding speed of the hybrid metal ion salt solution of 0.01mol/L ~ 5mol/L is 0.1mL/min ~ 1000mL/min, the OH of step 3 preparation ^-Concentration is that the adding speed of 0.1mol/L ~ 10mol/L precipitation reagent is 0.1mL/min ~ 1000mL/min, the NH of step 4 preparation ₄ ⁺Concentration is that the adding speed of 0.1mol/L ~ 10mol/L complexing agent is 0.1mL/min ~ 1000mL/min, the carbon nanomaterial concentration of step 5 preparation is that the adding speed of the carbon nanomaterial suspension of 0.1mg/L ~ 50g/L is 0.1mL/min ~ 500mL/min, and temperature be 20 ℃ ~ 90 ℃, mixing speed be 100rpm～10000rpm, pH be 5 ~ 13 and inert gas shielding under react, namely obtain the spherical precipitation thing; Seven, washing is dry processes: the spherical precipitation thing that at first adopts the washed with de-ionized water step 6 to obtain, clean be neutrality to the pH of filtrate till, then be 20 ℃ ~ 150 ℃ in temperature and be dried to constant weight, namely obtain the Uniform Doped carbon nanomaterial, molecular formula is Mn _αCo _βNi _γM _y(OH) ₂Metal hydroxides; Described Mn described in the step 1 _αCo _βNi _γM _y(OH) ₂In 0＜α≤1,0≤β≤1,0≤γ≤1,0≤y≤0.5, and alpha+beta+γ+y=1, β+γ＞0, wherein said Mn _αCo _βNi _γM _y(OH) ₂Middle M is a kind of or wherein several among Cr, Al, Fe, Mg, Ag, Ti, Cu, V, Y, La, Tm, Gd, Ho, Ce, Lu, Yb and the Sc; The volume of the reaction initial soln described in the step 6 and the volumetric ratio of reactor are (0.001 ~ 0.8): 1.

3. the preparation method of the presoma of a kind of doping carbon nano material according to claim 2 is characterized in that the soluble manganese salt described in the step 2 is a kind of in manganese sulfate, manganese nitrate, manganese chloride, manganese sulfate hydrate, manganese nitrate hydrate and the manganese chloride hydrate or several mixture wherein; Solubility cobalt salt described in the step 2 is a kind of in cobaltous sulfate, cobalt nitrate, cobalt chloride, cobaltous sulfate hydrate, cobalt nitrate hydrate and the cobalt chloride hydrate or several mixture wherein; Soluble nickel salt described in the step 2 is a kind of in nickelous sulfate, nickel nitrate, nickel chloride, nickelous sulfate hydrate, nickel nitrate hydrate and the nickel chloride hydrate or several mixture wherein; Soluble M salt described in the step 2 is a kind of in sulfuric acid M, nitric acid M, chlorination M, sulfuric acid M hydrate, nitric acid M hydrate and the chlorination M hydrate or several mixture wherein; Solvent described in the step 2 is deionized water, methanol aqueous solution, ethanol water, aqueous acetone solution, the methanol/ethanol aqueous solution, the methanol/acetone aqueous solution, the ethanol/acetone aqueous solution or methanol/ethanol/aqueous acetone solution; Solvent described in the step 3 is deionized water, methanol aqueous solution, ethanol water, aqueous acetone solution, the methanol/ethanol aqueous solution, the methanol/acetone aqueous solution, the ethanol/acetone aqueous solution or methanol/ethanol/aqueous acetone solution; Solubility hydroxide described in the step 3 is a kind of in NaOH, potassium hydroxide, lithium hydroxide and the barium hydroxide or several mixture wherein; Solubility ammonium salt described in the step 4 is a kind of in carbonic hydroammonium, ammonium carbonate, ammonium sulfate, ammonium hydrogen sulfate, ammonium chloride, ammonium phosphate, ammonium hydrogen phosphate and the ammonium dihydrogen phosphate or several mixture wherein; Solvent described in the step 4 is deionized water, methanol aqueous solution, ethanol water, aqueous acetone solution, the methanol/ethanol aqueous solution, the methanol/acetone aqueous solution, the ethanol/acetone aqueous solution or methanol/ethanol/aqueous acetone solution; Solvent described in the step 5 is deionized water, methanol aqueous solution, ethanol water, aqueous acetone solution, the methanol/ethanol aqueous solution, the methanol/acetone aqueous solution, the ethanol/acetone aqueous solution or methanol/ethanol/aqueous acetone solution; Carbon nanomaterial described in the step 5 is a kind of in carbon nano-tube, Graphene, graphene oxide, intercalated graphite alkene, carbon nano-fiber and the Nano carbon balls or several mixture wherein; Reaction initial soln described in the step 6 is to be configured to NH in solvent or employing solubility ammonium salt or the ammoniacal liquor adding solvent ₄ ⁺Concentration is the ammonia solution of 0.01mol/L ~ 2mol/L, wherein said solvent is deionized water, methanol aqueous solution, ethanol water, aqueous acetone solution, the methanol/ethanol aqueous solution, the methanol/acetone aqueous solution, the ethanol/acetone aqueous solution or methanol/ethanol/aqueous acetone solution, and wherein said solubility ammonium salt is a kind of in carbonic hydroammonium, ammonium carbonate, ammonium sulfate, ammonium hydrogen sulfate, ammonium chloride, ammonium phosphate, ammonium hydrogen phosphate and the ammonium dihydrogen phosphate or several mixture wherein; Inert gas described in the step 6 is argon gas, nitrogen or argon gas/nitrogen mixture body.

4. the preparation method of the presoma of a kind of doping carbon nano material as claimed in claim 1 is characterized in that the preparation method of the presoma of doping carbon nano material finishes according to the following steps: one, prepare raw material: according to chemical formula Mn _αCo _βNi _γM _yCO ₃By the Mn element: Co element: Ni element: M element mol ratio is that α: β: γ: y prepares soluble manganese salt, solubility cobalt salt, soluble nickel salt and soluble M salt; Two, preparation hybrid metal ion salt solution: soluble manganese salt, solubility cobalt salt, soluble nickel salt and soluble M salt that step 1 is prepared join in the solvent and mix, and being configured to the hybrid metal ion concentration is the hybrid metal ion salt solution of 0.01mol/L ~ 5mol/L; Three, preparation precipitation reagent: solubility hydroxide is added in the solvent, be configured to CO ₃ ^2-Concentration is 0.1mol/L ~ 10mol/L precipitation reagent; Four, preparation complexing agent: solubility ammonium salt or ammoniacal liquor are added in the solvent, be configured to NH ₄ ⁺Concentration is 0.1mol/L ~ 10mol/L complexing agent; Five, preparation carbon nanomaterial suspension: carbon nanomaterial is scattered in the solvent, and being configured to carbon nanomaterial concentration is the carbon nanomaterial suspension of 0.1mg/L ~ 50g/L; Six, coprecipitation reaction: the hybrid metal ion concentration that step 2 is prepared is the hybrid metal ion salt solution of 0.01mol/L ~ 5mol/L, the CO of step 3 preparation ₃ ^2-Concentration is the NH of 0.1mol/L ~ 10mol/L precipitation reagent, step 4 preparation ₄ ⁺Concentration is that the carbon nanomaterial concentration of 0.1mol/L ~ 10mol/L complexing agent and step 5 preparation is that the carbon nanomaterial suspension of 0.1mg/L ~ 50g/L adds in the reactor that the reaction initial soln is housed simultaneously, the hybrid metal ion concentration of step 2 preparation is that the adding speed of the hybrid metal ion salt solution of 0.01mol/L ~ 5mol/L is 0.1mL/min ~ 1000mL/min, the CO of step 3 preparation ₃ ^2-Concentration is that the adding speed of 0.1mol/L ~ 10mol/L precipitation reagent is 0.1mL/min ~ 1000mL/min, the NH of step 4 preparation ₄ ⁺Concentration is that the adding speed of 0.1mol/L ~ 10mol/L complexing agent is 0.1mL/min ~ 1000mL/min, the carbon nanomaterial concentration of step 5 preparation is that the adding speed of the carbon nanomaterial suspension of 0.1mg/L ~ 50g/L is 0.1mL/min ~ 500mL/min, and temperature be 20 ℃ ~ 90 ℃, mixing speed be 100rpm ~ 10000rpm, pH be 5 ~ 13 and inert gas shielding under react, namely obtain the spherical precipitation thing; Seven, washing is dry processes: the spherical precipitation thing that at first adopts the washed with de-ionized water step 6 to obtain, clean be neutrality to the pH of filtrate till, then be 20 ℃ ~ 150 ℃ in temperature and be dried to constant weight, namely obtain the Uniform Doped carbon nanomaterial, molecular formula is Mn _αCo _βNi _γM _yCO ₃Metal carbonate; Described Mn described in the step 1 _αCo _βNi _γM _yCO ₃In 0＜α≤1,0≤β≤1,0≤γ≤1,0≤y≤0.5, and alpha+beta+γ+y=1, β+γ＞0, wherein said Mn _αCo _βNi _γM _yCO ₃Middle M is a kind of or wherein several among Cr, Al, Fe, Mg, Ag, Ti, Cu, V, Y, La, Tm, Gd, Ho, Ce, Lu, Yb and the Sc; The volume of the reaction initial soln described in the step 6 and the volumetric ratio of reactor are (0.001 ~ 0.8): 1.

5. the preparation method of the presoma of a kind of doping carbon nano material according to claim 4 is characterized in that the soluble manganese salt described in the step 2 is a kind of in manganese sulfate, manganese nitrate, manganese chloride, manganese sulfate hydrate, manganese nitrate hydrate and the manganese chloride hydrate or several mixture wherein; Solubility cobalt salt described in the step 2 is a kind of in cobaltous sulfate, cobalt nitrate, cobalt chloride, cobaltous sulfate hydrate, cobalt nitrate hydrate and the cobalt chloride hydrate or several mixture wherein; Soluble nickel salt described in the step 2 is a kind of in nickelous sulfate, nickel nitrate, nickel chloride, nickelous sulfate hydrate, nickel nitrate hydrate and the nickel chloride hydrate or several mixture wherein; Soluble M salt described in the step 2 is a kind of in sulfuric acid M, nitric acid M, chlorination M, sulfuric acid M hydrate, nitric acid M hydrate and the chlorination M hydrate or several mixture wherein; Solvent described in the step 2 is deionized water, methanol aqueous solution, ethanol water, aqueous acetone solution, the methanol/ethanol aqueous solution, the methanol/acetone aqueous solution, the ethanol/acetone aqueous solution or methanol/ethanol/aqueous acetone solution; Solvent described in the step 3 is deionized water, methanol aqueous solution, ethanol water, aqueous acetone solution, the methanol/ethanol aqueous solution, the methanol/acetone aqueous solution, the ethanol/acetone aqueous solution or methanol/ethanol/aqueous acetone solution; Soluble carbonate salt described in the step 3 is a kind of in sodium carbonate, sodium acid carbonate, potash, ammonium carbonate and the carbonic hydroammonium or several mixture wherein; Solubility ammonium salt described in the step 4 is a kind of in carbonic hydroammonium, ammonium carbonate, ammonium sulfate, ammonium hydrogen sulfate, ammonium chloride, ammonium phosphate, ammonium hydrogen phosphate and the ammonium dihydrogen phosphate or several mixture wherein; Solvent described in the step 4 is deionized water, methanol aqueous solution, ethanol water, aqueous acetone solution, the methanol/ethanol aqueous solution, the methanol/acetone aqueous solution, the ethanol/acetone aqueous solution or methanol/ethanol/aqueous acetone solution; Solvent described in the step 5 is deionized water, methanol aqueous solution, ethanol water, aqueous acetone solution, the methanol/ethanol aqueous solution, the methanol/acetone aqueous solution, the ethanol/acetone aqueous solution or methanol/ethanol/aqueous acetone solution; Carbon nanomaterial described in the step 5 is a kind of in carbon nano-tube, Graphene, graphene oxide, intercalated graphite alkene, carbon nano-fiber and the Nano carbon balls or several mixture wherein; Reaction initial soln described in the step 6 is to be configured to NH in solvent or employing solubility ammonium salt or the ammoniacal liquor adding solvent ₄ ⁺Concentration is the ammonia solution of 0.01mol/L ~ 2mol/L, wherein said solvent is deionized water, methanol aqueous solution, ethanol water, aqueous acetone solution, the methanol/ethanol aqueous solution, the methanol/acetone aqueous solution, the ethanol/acetone aqueous solution or methanol/ethanol/aqueous acetone solution, and wherein said solubility ammonium salt is a kind of in carbonic hydroammonium, ammonium carbonate, ammonium sulfate, ammonium hydrogen sulfate, ammonium chloride, ammonium phosphate, ammonium hydrogen phosphate and the ammonium dihydrogen phosphate or several mixture wherein; Inert gas described in the step 6 is argon gas, nitrogen or argon gas/nitrogen mixture body.

6. a spherical lithium metal oxide positive electrode is characterized in that spherical lithium metal oxide positive electrode is prepared from by the presoma of lithium-containing compound and doping carbon nano material claimed in claim 1; The ratio of the amount of the Li elemental substance in the presoma of described doping carbon nano material in the total amount of substance of metallic element and the described lithium-containing compound is 1:(1 ~ 1.42); The presoma of described doping carbon nano material is that Uniform Doped carbon nanomaterial, molecular formula are Mn _αCo _βNi _γM _y(OH) ₂Metal hydroxides or Uniform Doped carbon nanomaterial, molecular formula be Mn _αCo _βNi _γM _yCO ₃Metal carbonate; Wherein said Mn _αCo _βNi _γM _y(OH) ₂In 0＜α≤1,0≤β≤1,0≤γ≤1,0≤y≤0.5, and alpha+beta+γ+y=1, β+γ＞0, described Mn _αCo _βNi _γM _y(OH) ₂Middle M is a kind of or wherein several among Cr, Al, Fe, Mg, Ag, Ti, Cu, V, Y, La, Tm, Gd, Ho, Ce, Lu, Yb and the Sc; Wherein said Mn _αCo _βNi _γM _yCO ₃In 0＜α≤1,0≤β≤1,0≤γ≤1,0≤y≤0.5, and alpha+beta+γ+y=1, β+γ＞0, described Mn _αCo _βNi _γM _yCO ₃Middle M is a kind of or wherein several among Cr, Al, Fe, Mg, Ag, Ti, Cu, V, Y, La, Tm, Gd, Ho, Ce, Lu, Yb and the Sc.

7. a kind of spherical lithium metal oxide positive electrode according to claim 6 is characterized in that described lithium-containing compound is a kind of in lithium hydroxide, lithium carbonate, lithium acetate, lithium oxalate, lithium nitrate and the lithium citrate or several mixture wherein.

8. the preparation method of a kind of spherical lithium metal oxide positive electrode as claimed in claim 6, the preparation method who it is characterized in that spherical lithium metal oxide positive electrode finishes according to the following steps: one, presoma preliminary treatment: the presoma of doping carbon nano material claimed in claim 1 at 200 ℃ ~ 800 ℃ pre-burning 1h～12h, is obtained presoma after the preliminary treatment; Two, mixed lithium sintering: presoma after the preliminary treatment is mixed with lithium-containing compound, is 600 ℃～1200 ℃ roasting 3h ~ 36h in temperature then, cools to room temperature with the furnace and namely obtains spherical lithium metal oxide positive electrode; The presoma of the doping carbon nano material described in the step 1 is that Uniform Doped carbon nanomaterial, molecular formula are Mn _αCo _βNi _γM _y(OH) ₂Metal hydroxides or Uniform Doped carbon nanomaterial, molecular formula be Mn _αCo _βNi _γM _yCO ₃Metal carbonate; Wherein said Mn _αCo _βNi _γM _y(OH) ₂In 0＜α≤1,0≤β≤1,0≤γ≤1,0≤y≤0.5, and alpha+beta+γ+y=1, β+γ＞0, described Mn _αCo _βNi _γM _y(OH) ₂Middle M is a kind of or wherein several among Cr, Al, Fe, Mg, Ag, Ti, Cu, V, Y, La, Tm, Gd, Ho, Ce, Lu, Yb and the Sc; Wherein said Mn _αCo _βNi _γM _yCO ₃In 0＜α≤1,0≤β≤1,0≤γ≤1,0≤y≤0.5, and alpha+beta+γ+y=1, β+γ＞0, described Mn _αCo _βNi _γM _yCO ₃Middle M is a kind of or wherein several among Cr, Al, Fe, Mg, Ag, Ti, Cu, V, Y, La, Tm, Gd, Ho, Ce, Lu, Yb and the Sc; The ratio of the amount of the Li elemental substance in the presoma of the doping carbon nano material described in the step 1 in the total amount of substance of metallic element and the lithium-containing compound described in the step 2 is 1:(1 ~ 1.42).

9. the preparation method of a kind of spherical lithium metal oxide positive electrode according to claim 8 is characterized in that a kind of in lithium-containing compound lithium hydroxide, lithium carbonate, lithium acetate, lithium oxalate, lithium nitrate and the lithium citrate described in the step 2 or several mixture wherein.