CN100342568C - Method for producing anode active material containing lithium, magnesium compound oxide - Google Patents
Method for producing anode active material containing lithium, magnesium compound oxide Download PDFInfo
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- CN100342568C CN100342568C CNB200510015096XA CN200510015096A CN100342568C CN 100342568 C CN100342568 C CN 100342568C CN B200510015096X A CNB200510015096X A CN B200510015096XA CN 200510015096 A CN200510015096 A CN 200510015096A CN 100342568 C CN100342568 C CN 100342568C
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Abstract
The present invention relates to a method for preparing multipleunit active material of an anode with lithium magnesium compound oxide, which relates to an electrode which is formed by the method that lithium manganese oxide is selected to serve as one of active material. The method has a step sequence that M (OH) 2 can be prepared directly by a lithium hydroxide coprecipitation method, the M (OH) 2 and lithium salt are mixed in by a ball milling method, are tableted, and are preroasted, and a ball milling tablet is cooled and then roasted into a finished product. Nickel salt used in the preparation method is nickel acetate or nickel nitrate, the used cobalt salt is Cobalt acetate or cobalt nitrate, the used manganese salt is manganese nitrate or manganese acetate, and the used lithium salt is lithium carbonate, lithium hydroxide or lithium acetate. In the method, a coprecipitation process can be also controlled by the adoption of ammonia and oxalate in the step that the M (OH) 2 is prepared by a coprecipitation method, lower alcohol can be added in when the ball milling is carried out in the step that the ball milling tablet is cooled, and in the step that the M (OH) 2 is prepared by the coprecipitation method, the doped sesquioxide aluminum or titanium dioxide are added in. The method of the present invention has the advantage of simple synthesis technology, and overcomes the defects that the capacity of cathode material made by the prior art is lower and is attenuated seriously at a high temperature.
Description
Technical field
Technical scheme of the present invention relates to a kind of electrode of selecting lithium manganese oxide as one of active material, specifically the preparation method of the anode active material of lithium-magnesium containing composite oxides in the lithium ion battery.
Background technology
Battery is the indispensable energy parts of many portable equipments.Lithium ion battery is compared with other chargeable batteries, has higher energy density and cycle performance.Because electronic product, electric automobile and various be the develop rapidly of the product of the energy with the battery, driven the increase of lithium ion battery demand.Business-like lithium ion battery mainly is with stratiform LiCoO
2Be positive electrode, but cobalt resource scarcity, poisonous, contaminated environment and cost an arm and a leg have limited further developing of lithium ion battery, force people to be devoted to development and can replace LiCoO
2, well behaved, environment amenable anode material for lithium-ion batteries, particularly be concerned about the composite oxides of other metals and lithium.Wherein, lithium manganese oxide is with its good stability, nontoxic pollution-free, outstanding advantage that operating voltage is high, and the manganese low price, and china natural resources is abundant relatively, has become a kind of anode material for lithium-ion batteries that is expected.In recent years, people have carried out big quantity research: WO 2005005319 " anode material for lithium-ion batteries " to the lithium manganese oxide as anode material for lithium-ion batteries and disclose the method for preparing the mealy crystal metal oxide materials that contains two or three kind of equally distributed metallic element, are to resolve into multiple metal oxide crystal mixture by the roasting in air of inorganic acid salt powder; US 2004115534 provides preparation to be used for the method for the Li-Mn-Ni composite oxides of lithium ion secondary battery anode material, may further comprise the steps: (a) lithium salts, manganese salt and nickel salt are dissolved in distilled water and form the aqueous solution, (b) add hydrothermal solution and form gel, (c) calcining preparing gel oxide powder, (d) oxide powder is carried out the heat treatment first time, grind the product of gained, (e) products therefrom is carried out the heat treatment second time, grind the product of gained again; CN 200410005732.6 discloses a kind of preparation method of lithium manganese oxide and the application in battery thereof, and its method is to adopt the synthetic lithium manganese oxide of low temperature double sintering method; CN 200410009004.2 discloses a kind of spherical lithium manganate and preparation method, it is characterized in that at first manganese sulfate or manganese chloride or manganese nitrate and permanganate or peroxydisulfate being reacted and adding the removal of impurities additive in liquid phase medium, pH value, temperature, charging rate, the generation spherical manganese dioxide of control reactant liquor, it is dry to mix the back with spherical manganese dioxide and LITHIUM BATTERY lithium hydroxide or lithium nitrate or lithium carbonate and zinc or aluminium or zirconium in organic solvent again, then dry thing calcining is generated spherical lithium manganate; CN 200410026480.5 relates to a kind of lithium ion battery composite cathode material and preparation method thereof, and this invention is mixed with colloidal sol with needed raw material, then with reducing agent with the metal ions M in the colloidal sol
N+Be reduced into metal simple-substance, formed gel after the colloidal sol drying is calcined in inert gas atmosphere, make the organic substance in the gel be cracked into conductive carbon black, ferric phosphate (II) lithium, metal simple-substance have formed the lithium ion battery composite material jointly with carbon black like this; Positive electrode active materials of the secondary cell that CN 02820669.X discloses and preparation method thereof, its main technique be with raw material at 700～1000 ℃ of temperature lower calcinations, cooling then; CN 03156756.8 a kind of lithium ion battery layer pole structure manganate cathode material for lithium of report and intercalation process for assembly preparing thereof, the preparation method of this positive electrode is: adopt earlier the oxidized inserting layer method to prepare the stratiform manganate precursor for lithium, again by ion-exchange reactions with the part lithium ion Li in the layered lithium manganate electrode material
+Use alkaline-earth metal ions Mg
2+, Ca
2+Or Sr
2+Replacement is with prepared layer post LiMn2O4.The shortcoming of above-mentioned prior art is: synthesis technique complexity not only, and the lithium manganese oxide that is made by these methods is on the low side as the capacity of the positive electrode of lithium ion battery, and capacity attenuation is serious under the high temperature, and its range of application still is subjected to certain restriction.
Summary of the invention
Technical problem to be solved by this invention is: the preparation method that a kind of anode active material of lithium-magnesium containing composite oxides is provided, its synthesis technique is simple, and it is on the low side to have overcome the positive electrode capacity that prior art makes, capacity attenuation important disadvantages under the high temperature.
The present invention solves this technical problem the technical scheme that is adopted: the preparation method of the anode active material of lithium-magnesium containing composite oxides of the present invention the steps include:
The first step, coprecipitation prepare M (OH)
2
At first at normal temperatures and pressures, according to stoichiometry preparation soluble nickel salt, mixed liquor 0.1～the 1M of cobalt salt and manganese salt, flow velocity with 0.3ml/min is added drop-wise in the lithium hydroxide solution that concentration is 2mol/l, react, adopt ammoniacal liquor and oxalic acid control coprecipitation process simultaneously, concrete operations are, in precipitation process, add proper ammonia and oxalic acid, to with metal ion take place simultaneously to precipitate fully with network and chemical reaction, the control reaction pH value is 8～13, and the sediment that reaction is obtained filters out, and uses deionized water to clean repeatedly up to pH value to reach neutrality, sediment vacuumize, make coprecipitate M (OH) then
2, the M here comprises Ni, Co and Mn;
In second step, mix with the lithium salts ball milling
The coprecipitate M (OH) that the first step is made
2According to M (OH)
2: the mol ratio of lithium salts=1: 1～1.1 adds lithium salts and carries out the ball milling mixing, makes the mixed-powder that contains Li and M;
The 3rd step, compressing tablet and preroast
With the hydraulic press lower sheeting of second mixed-powder that contains Li and M that make of step, the sheet that presses is positioned in the muffle furnace under 480 ℃ of temperature, carries out 3 hours preroast again at 50MPa pressure;
The 4th step, cooling ball milling compressing tablet
Carry out the ball milling powdered again behind the product cool to room temperature with the 3rd preroast that makes of step, then at the hydraulic press lower sheeting of 50MPa pressure;
In the 5th step, roasting becomes product
The compressing tablet that the 4th step was made places muffle furnace 4～9 hours 500～900 ℃ of roasting temperature times, makes the anode active material of lithium-magnesium containing composite oxides.
Used nickel salt is nickel acetate or nickel nitrate among the preparation method of the anode active material of lithium-magnesium containing composite oxides of the present invention; Used cobalt salt is cobalt acetate or cobalt nitrate; Used manganese salt is manganese nitrate or manganese acetate; Used lithium salts is lithium carbonate, lithium hydroxide or lithium acetate.
Add lower alcohol when in the 4th step cooling ball milling compressing tablet step of said method, carrying out ball milling; The lower alcohol that is added is ethanol, methyl alcohol, propyl alcohol or butanols.
Said method first step coprecipitation prepare M (OH)
2In the step, add the alundum (Al or alundum (Al and the titanium dioxide that mix, the adding method is: prepare M (OH) in the first step
2In the step, on basis according to the cobalt acetate consumption among the mixed liquor 0.1～1M of stoichiometry preparation solubility nickel acetate, cobalt acetate and manganese acetate, reduce 1/12 cobalt element amount in this mixed liquor, the coprecipitate after the vacuumize and addition are mixed for the solid-state aluminium hydroxide of the cobalt amount that reduces or a semisolid aluminium hydroxide and half solid titania.
The invention has the beneficial effects as follows: the inventive method and prior art have significant difference and significantly progressive, and what the present invention adopted is coprecipitation and sol-gel process.Coprecipitation and sol-gel process are advanced material synthesis method, be widely used in preparing products such as various ceramic powders, film, coating, fiber, the outstanding advantage of this method is, each component of raw material can reach the even mixing of atom level, and the chemical uniformity of product is good, the purity height, stoichiometric proportion can accurately be controlled, heat treatment temperature can significantly reduce, and heat treatment time can significantly shorten, and might realize the structure of material is accurately cut out by control process parameters.Therefore, the anode material for lithium-ion batteries that adopts this method to synthesize has been optimized composition, the structure of material, has improved material electrochemical performance; The inventive method synthesis technique is simple, has reduced preparation cost.More outstanding is the method that the present invention directly uses the lithium hydroxide co-precipitation, and with ammoniacal liquor and oxalic acid control coprecipitation process, ammoniacal liquor or oxalic acid are a kind of complexing agents, form complex ion with metal simultaneously.The effect that adds complexing agent mainly shows both ways, is that complexing agent is for M (OH) on the one hand
2The control action of (M=Mn, Ni, Co here) nucleus formation speed.The formation of metal complex ion has weakened central ion M
2+Polarization, thereby also just alleviated it and OH
-Effect between the ion, the speed of growth of nucleus when having reduced the reaction beginning effectively makes nucleus have time enough to grow up and align in lattice, thereby makes the M (OH) of generation
2Precipitation particles not only particle diameter is bigger, and compact crystallization, crystal degree are higher; Effect shows its influence to the crystal growth process on the other hand, and it not only helps growing up of crystal, and the sphericity of crystal grain is improved, and makes pre-crystallization better.Add lower alcohol after the pre-burning and grind, make the ball milling uniform particles, good dispersion degree.The calcining temperature programming of the inventive method, temperature is lower than general bibliographical information, saves the energy.In addition, the oxide of doping plays the effect that improves voltage platform, stable crystal structure, raising thermal stability.
LiMn
2O
4Begin at wherein manganese more than 55 ℃ dissolved, thereby the activity that causes collecting material reduces.Someone uses sol-gal process to make this material, but manufacture craft comparatively complexity and cost are higher, the tap density of obtained material is lower simultaneously, is unfavorable for the application of material on battery industry.Not only capacity is higher for the prepared material of the present invention, and its granularity and pattern are better, and have overcome LiNiO
2The shortcoming that need prepare under oxygen atmosphere, it has kept LiNiO simultaneously
2The characteristics of material high power capacity.
Description of drawings
The present invention is further described below in conjunction with drawings and Examples.
Fig. 1 is the anode active material preparation method's of a lithium-magnesium containing composite oxides of the present invention flow chart.
Fig. 2 is 6 hours gained sample LiNi of 700 ℃ of calcinings
1/3Co
1/3Mn
1/3O
2Sem photograph.
Fig. 3 is 6 hours gained sample LiNi of 800 ℃ of calcinings
1/3Co
1/3Mn
1/3O
2Sem photograph.
Fig. 4 is 6 hours gained sample LiNi of 900 ℃ of calcinings
1/3Co
1/3Mn
1/3O
2Sem photograph.
Fig. 5 is 700 ℃, 800 ℃ and 6 hours products therefrom LiNi of 900 ℃ of sintering temperatures
1/3Co
1/3Mn
1/3O
2Preceding twice charging and discharging curve.
Fig. 6 is at 9 hours following LiNi of 800 ℃ of roastings
1/3Co
1/3Mn
1/3O
2The charge and discharge cycles curve.
Fig. 7 is LiNi
1/3Co
1/4Mn
1/3Al
1/2O
2, LiNi
1/3Co
1/4Mn
1/3Ti
1/12O
2Preceding twice charging and discharging curve.
Embodiment
Fig. 1 illustrate salting liquid that the anode active material preparation method of lithium-magnesium containing composite oxides of the present invention comprises Ni, Co, Mn with Li aqueous slkali reaction co-precipitation, mix with the lithium salts ball milling, compressing tablet and preroast, cooling ball milling compressing tablet and five step of roasting operation, as seen the inventive method synthesis technique is simple.
Fig. 2 illustrates 6 hours gained sample LiNi of 700 ℃ of calcinings
1/3Co
1/3Mn
1/3O
2Distribution of particles is comparatively even, has certain agglomeration.
Fig. 3 illustrates 6 hours gained sample LiNi of 800 ℃ of calcinings
1/3Co
1/3Mn
1/3O
2The single particle degree is less, and pattern is rule comparatively, and the smooth cycle performance that helps improving material of particle surface has certain agglomeration to take place.
Fig. 4 illustrates 6 hours gained sample LiNi of 900 ℃ of calcinings
1/3Co
1/3Mn
1/3O
2Particle is bigger, and agglomeration is serious.
Fig. 5 illustrates that when calcining heat was 700 ℃, the product reversible capacity was less, increases to some extent by improving the calcining heat capacity thereupon; When calcining heat was 900 ℃, the capacity of product was higher, and discharge capacity is more than 150mAh/g.
Fig. 6 illustrates battery after 15 circulations, and big discharge capacity does not have tangible capacity attenuation, shows that this material has excellent cycle performance, and it has improved the cyclical stability of battery.
The doping that Fig. 7 illustrates Al has certain effect to the raising of current potential, and the doping of Ti has improved the chemical property of material.
Embodiment 1
At normal temperatures and pressures, mixed liquor 0.1M according to stoichiometry preparation nickel acetate, cobalt acetate and manganese nitrate, flow velocity with 0.3ml/min is added drop-wise in the lithium hydroxide solution that concentration is 2mol/l, react, the control reaction pH value is 8, and the sediment that reaction is obtained filters out, and uses deionized water to clean repeatedly up to pH value to reach neutrality, sediment vacuumize, make coprecipitate M (OH) then
2, the M here comprises Ni, Co and Mn; With prepared coprecipitate M (OH)
2According to M (OH)
2: the mol ratio of lithium carbonate=1: 1 adds lithium carbonate carries out ball milling and mixes, and makes the mixed-powder that contains Li and M; With the prepared hydraulic press lower sheeting that contains the mixed-powder of Li and M at 50MPa pressure, the sheet that presses is positioned in the muffle furnace under 480 ℃ of temperature, carries out 3 hours preroast again; The ball milling powdered will be carried out again, then at the hydraulic press lower sheeting of 50MPa pressure behind the product cool to room temperature of prepared preroast; Place muffle furnace 4 hours 500 ℃ of roasting temperature times prepared compressing tablet, make the anode active material of lithium-magnesium containing composite oxides.
Embodiment 2
At normal temperatures and pressures, mixed liquor 0.5M according to stoichiometry preparation solubility nickel nitrate, cobalt nitrate and manganese acetate, flow velocity with 0.3ml/min is added drop-wise in the lithium hydroxide solution that concentration is 2mol/l, react, the control reaction pH value is 10, and the sediment that reaction is obtained filters out, and uses deionized water to clean repeatedly up to pH value to reach neutrality, sediment vacuumize, make coprecipitate M (OH) then
2, the M here comprises Ni, Co and Mn; With prepared coprecipitate M (OH)
2According to M (OH)
2: the mol ratio of lithium hydroxide=1: 1 adds lithium hydroxide carries out ball milling and mixes, and makes the mixed-powder that contains Li and M; With the prepared hydraulic press lower sheeting that contains the mixed-powder of Li and M at 50MPa pressure, the sheet that presses is positioned in the muffle furnace under 480 ℃ of temperature, carries out 3 hours preroast again; The ball milling powdered will be carried out again, then at the hydraulic press lower sheeting of 50MPa pressure behind the product cool to room temperature of prepared preroast; Place muffle furnace 6 hours 700 ℃ of roasting temperature times prepared compressing tablet, make the anode active material of lithium-magnesium containing composite oxides, gained LiNi
1/3Co
1/3Mn
1/3O
2Sem photograph see Fig. 2.
Embodiment 3
Except that prepared compressing tablet being placed muffle furnace 800 ℃ of roasting temperatures 6 hours, other are all with embodiment 2, gained LiNi
1/3Co
1/3Mn
1/3O
2Sem photograph see Fig. 3.
Embodiment 4
Except that prepared compressing tablet being placed muffle furnace 900 ℃ of roasting temperatures 6 hours, other are all with embodiment 2, gained LiNi
1/3Co
1/3Mn
1/3O
2Sem photograph see Fig. 4.
At embodiment 3,4 and 5, Fig. 5 explanation: in the time of 700 ℃, the product reversible capacity is less, increases to some extent by improving the calcining heat capacity thereupon.When calcining heat was 900 ℃, the capacity of product was higher, and discharge capacity is more than 150mAh/g.
Embodiment 5
At normal temperatures and pressures, mixed liquor 1M according to stoichiometry preparation solubility nickel nitrate, cobalt acetate and manganese acetate, flow velocity with 0.3ml/min is added drop-wise in the lithium hydroxide solution that concentration is 2mol/l, react, the control reaction pH value is 13, and the sediment that reaction is obtained filters out, and uses deionized water to clean repeatedly up to pH value to reach neutrality, sediment vacuumize, make coprecipitate M (OH) then
2, the M here comprises Ni, Co and Mn; With prepared coprecipitate M (OH)
2According to M (OH)
2: the mol ratio of lithium acetate=1: 1.1 adds lithium acetate carries out ball milling and mixes, and makes the mixed-powder that contains Li and M; With the prepared hydraulic press lower sheeting that contains the mixed-powder of Li and M at 50MPa pressure, the sheet that presses is positioned in the muffle furnace under 480 ℃ of temperature, carries out 3 hours preroast again; The ball milling powdered will be carried out again, then at the hydraulic press lower sheeting of 50MPa pressure behind the product cool to room temperature of prepared preroast; Place muffle furnace 9 hours 800 ℃ of roasting temperature times prepared compressing tablet, make the anode active material of lithium-magnesium containing composite oxides.Fig. 6 is this material LiNi
1/3Co
1/3Mn
1/3O
2Charge and discharge cyclic curve, the battery that its explanation is made of its is after 15 circulations, big discharge capacity does not have tangible capacity attenuation, shows that this material has excellent cycle performance, it has improved the cyclical stability of battery.
Embodiment 6
At normal temperatures and pressures, preparing the solubility nickel acetate according to stoichiometry, on the basis of the cobalt acetate consumption among the mixed liquor 1M of cobalt acetate and manganese acetate, reduce 1/12 cobalt element amount in the mixed liquor, the consumption of nickel acetate and manganese acetate is constant, the flow velocity with 0.3ml/min of liquid mixture prepared thus is added drop-wise in the lithium hydroxide solution that concentration is 2mol/l, add proper ammonia and oxalic acid simultaneously, to with metal ion take place simultaneously to precipitate fully with network and chemical reaction, the control reaction pH value is 9, the sediment that reaction is obtained filters out, and use deionized water to clean repeatedly and reach neutral up to the pH value, sediment vacuumize, make coprecipitate M (OH) then
2, the M here comprises Ni, Co and Mn, and the coprecipitate after the vacuumize and the addition solid-state aluminium hydroxide for the cobalt amount that reduces is mixed; With prepared coprecipitate according to M (OH)
2: the mol ratio of lithium hydroxide=1: 1 adds lithium hydroxide carries out ball milling and mixes, and makes the mixed-powder that contains Li, M and Al; With the hydraulic press lower sheeting of prepared mixed-powder, the sheet that presses is positioned in the muffle furnace under 480 ℃ of temperature, carries out 3 hours preroast again at 50MPa pressure; To carry out the ball milling powdered behind the product cool to room temperature of prepared preroast again, add ethanol in the time of ball milling, then at the hydraulic press lower sheeting of 50MPa pressure; Place muffle furnace 9 hours 900 ℃ of roasting temperature times prepared compressing tablet, make the anode active material of the lithium-magnesium containing composite oxides of doped aluminium.
Embodiment 7
Remove solid-state aluminium hydroxide is replaced with solid titania, ethanol replaces with outside the propyl alcohol, and other make the anode active material of the lithium-magnesium containing composite oxides of adulterated TiOx all with embodiment 6.
Fig. 7 is LiNi
1/3Co
1/4Mn
1/3Al
1/12O
2, LiNi
1/3Co
1/4Mn
1/3Ti
1/12O
2Preceding twice charging and discharging curve, the doping of its explanation Al has certain effect to the raising of current potential, and the doping of Ti has improved the chemical property of material.
Embodiment 8
Except that solid-state aluminium hydroxide being replaced with solid-state aluminium hydroxide and solid titania each half, other are all with embodiment 6, make the anode active material of the lithium-magnesium containing composite oxides of doped aluminium and titanium oxide simultaneously.
Embodiment 9
Except that ethanol is replaced with the methyl alcohol, other make the anode active material of the lithium-magnesium containing composite oxides of doped aluminium all with embodiment 6.
Except that ethanol is replaced with the butanols, other make the anode active material of the lithium-magnesium containing composite oxides of adulterated TiOx all with embodiment 7.
Claims (4)
1. the preparation method of the anode active material of lithium-magnesium containing composite oxides is characterized in that: step is,
The first step, coprecipitation prepare M (OH)
2
At first at normal temperatures and pressures, according to stoichiometry preparation soluble nickel salt, mixed liquor 0.1～the 1M of cobalt salt and manganese salt, flow velocity with 0.3ml/min is added drop-wise in the lithium hydroxide solution that concentration is 2mol/l, react, adopt ammoniacal liquor and oxalic acid control coprecipitation process simultaneously, concrete operations are, in precipitation process, add proper ammonia and oxalic acid, to with metal ion take place simultaneously to precipitate fully with network and chemical reaction, the control reaction pH value is 8～13, and the sediment that reaction is obtained filters out, and uses deionized water to clean repeatedly up to pH value to reach neutrality, sediment vacuumize, make coprecipitate M (OH) then
2, the M here comprises Ni, Co and Mn;
In second step, mix with the lithium salts ball milling
The coprecipitate M (OH) that the first step is made
2According to M (OH)
2: the mol ratio of lithium salts=1: 1～1.1 adds lithium salts and carries out the ball milling mixing, makes the mixed-powder that contains Li and M;
The 3rd step, compressing tablet and preroast
With the hydraulic press lower sheeting of second mixed-powder that contains Li and M that make of step, the sheet that presses is positioned in the muffle furnace under 480 ℃ of temperature, carries out 3 hours preroast again at 50MPa pressure;
The 4th step, cooling ball milling compressing tablet
Carry out the ball milling powdered again behind the product cool to room temperature with the 3rd preroast that makes of step, add lower alcohol in the time of ball milling, then at the hydraulic press lower sheeting of 50MPa pressure;
In the 5th step, roasting becomes product
The compressing tablet that the 4th step was made places muffle furnace 4～9 hours 500～900 ℃ of roasting temperature times, makes the anode active material of lithium-magnesium containing composite oxides.
2. according to the preparation method of the anode active material of the described lithium-magnesium containing composite oxides of claim 1, it is characterized in that: used nickel salt is nickel acetate or nickel nitrate; Used cobalt salt is cobalt acetate or cobalt nitrate; Used manganese salt is manganese nitrate or manganese acetate; Used lithium salts is lithium carbonate, lithium hydroxide or lithium acetate.
3. according to the preparation method of the anode active material of the described lithium-magnesium containing composite oxides of claim 1, it is characterized in that: the lower alcohol that is added is ethanol, methyl alcohol, propyl alcohol or butanols.
4. according to the preparation method of the anode active material of the described lithium-magnesium containing composite oxides of claim 1, it is characterized in that: said method first step coprecipitation prepare M (OH)
2In the step, add the alundum (Al or alundum (Al and the titanium dioxide that mix, the adding method is: prepare M (OH) in the first step
2In the step, on basis according to the cobalt acetate consumption among the mixed liquor 0.1～1M of stoichiometry preparation solubility nickel acetate, cobalt acetate and manganese acetate, reduce 1/12 cobalt element amount in this mixed liquor, the coprecipitate after the vacuumize and addition are mixed for the solid-state aluminium hydroxide of the cobalt amount that reduces or a semisolid aluminium hydroxide and half solid titania.
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| CN102239588B (en) * | 2008-12-24 | 2014-09-24 | 日本碍子株式会社 | Plate-shaped particles for positive electrode material of lithium secondary batteries, lithium secondary battery positive electrode active material films, manufacturing method therefor, lithium secondary battery positive electrode active material man |
| CN102239587B (en) * | 2008-12-24 | 2015-11-25 | 日本碍子株式会社 | The manufacture method of the platy particles of the positive active material of lithium secondary battery, the positive electrode active material films of lithium secondary battery, their manufacture method, the positive active material of lithium secondary battery and lithium secondary battery |
| WO2010074299A1 (en) * | 2008-12-24 | 2010-07-01 | 日本碍子株式会社 | Plate-shaped particles for positive electrode active material of lithium secondary batteries, and lithium secondary batteries |
| JP4703786B2 (en) | 2008-12-24 | 2011-06-15 | 日本碍子株式会社 | Plate-like particle for positive electrode active material of lithium secondary battery, same material film, and lithium secondary battery |
| CN101863519B (en) * | 2010-06-13 | 2012-04-04 | 浙江亿利泰钴镍材料有限公司 | Preparation method for nickel-cobalt-manganese ternary hydroxide for lithium battery and product |
| CN102120624B (en) * | 2011-01-14 | 2013-01-23 | 哈尔滨工业大学 | Method for preparing high-voltage lithium ion battery positive electrode material LiXyNi0.5-yMn1.5O4 |
| CN102569780B (en) * | 2012-02-28 | 2014-04-09 | 南京航空航天大学 | Method for preparing lithium ion battery cathode material with layered structure |
| CN104835956A (en) * | 2015-01-16 | 2015-08-12 | 四川大学 | Method of preparing lithium ion battery anode material from two or more metal salts/solutions of nickel, cobalt, manganese, aluminum and the like |
| CN106564967B (en) * | 2016-10-31 | 2018-06-05 | 安泰科技股份有限公司 | Lithium-rich manganese-based anode material presoma, positive electrode and preparation method thereof |
| CN112582604B (en) * | 2020-03-18 | 2023-07-18 | 新余学院 | Modification method of high-nickel ternary lithium battery anode material |
| CN114583159B (en) * | 2022-02-24 | 2023-08-04 | 合肥国轩高科动力能源有限公司 | Low-temperature lithium iron phosphate positive electrode material, preparation method and application thereof |
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| CN1545159A (en) * | 2003-11-25 | 2004-11-10 | 复旦大学 | Method for preparing positive electrode material LiNixMn1-xO2 of lithium ion battery |
| CN1612378A (en) * | 2003-10-28 | 2005-05-04 | 大同股份有限公司 | Method for manufacturing lithiumi on secondary cell anode material |
| CN1614801A (en) * | 2003-11-07 | 2005-05-11 | 中国科学院上海微系统与信息技术研究所 | Multi-component composite positive material for lithium ion battery and preparing method thereof |
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2005
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1389939A (en) * | 2001-06-04 | 2003-01-08 | 中国科学院成都有机化学研究所 | Method of synthesizing LiCo1-xMxO2 as positive electrode material for lithium ion accmulator |
| CN1612378A (en) * | 2003-10-28 | 2005-05-04 | 大同股份有限公司 | Method for manufacturing lithiumi on secondary cell anode material |
| CN1614801A (en) * | 2003-11-07 | 2005-05-11 | 中国科学院上海微系统与信息技术研究所 | Multi-component composite positive material for lithium ion battery and preparing method thereof |
| CN1545159A (en) * | 2003-11-25 | 2004-11-10 | 复旦大学 | Method for preparing positive electrode material LiNixMn1-xO2 of lithium ion battery |
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