CN106207178A - The preparation method of positive electrode, positive electrode and battery - Google Patents
The preparation method of positive electrode, positive electrode and battery Download PDFInfo
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- CN106207178A CN106207178A CN201510218116.7A CN201510218116A CN106207178A CN 106207178 A CN106207178 A CN 106207178A CN 201510218116 A CN201510218116 A CN 201510218116A CN 106207178 A CN106207178 A CN 106207178A
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Abstract
Present invention is disclosed the preparation method of a kind of positive electrode, comprise the following steps: lithium source is dissolved in the mixed solvent of deionized water and ethylene glycol and obtains the first solution, phosphorus source is dissolved in ethylene glycol and obtains the second solution, by Organic substance, source of iron or/and manganese source is dissolved in the mixed solvent of deionized water and ethylene glycol acquisition the 3rd solution, wherein lithium source, source of iron, manganese source, phosphorus source mix than 3:1-x:x:1 according to the amount of the material of Li, Fe, Mn, P, wherein 0≤x≤1；Second solution is joined in the first solution and obtain the first suspension, the 3rd solution is joined the first suspension obtains the second suspension；Being sealed in water heating kettle by second suspension and carry out hydro-thermal reaction, washing is dried to obtain positive electrode.Present invention further teaches a kind of positive electrode and a kind of battery.The positive electrode of granule-morphology uniform particle diameter can be prepared by the preparation method of the present invention.
Description
Technical field
The invention belongs to field of batteries, be specifically related to the preparation method of a kind of positive electrode.
The invention still further relates to a kind of positive electrode and use the battery of this positive electrode.
Background technology
The eighties in 20th century, scientists was to find environmentally friendly new energy materials, at lithium primary cell
On the basis of developed can the lithium secondary battery of discharge and recharge.The lithium ion battery being well recognized as due to positive electrode
In the most key material, its performance quality will directly affect battery properties (energy storage density, circulation longevity
Life, safety etc.), so its development merits attention most.
At Goodenough etc., stratiform cobalt acid lithium (LiCoO is proposed2) as positive electrode and by Sony company
After nineteen ninety realizes Commercialization application, people are found that other anode material for lithium-ion batteries in succession,
Lithium nickelate (LiNiO such as stratiform2), LiMn2O4 (LiMnO2), nickle cobalt lithium manganate (Li (Ni, Co, Mn) O2)、
Lithium manganate having spinel structure (LiMn2O4) and olivine-type LiFePO4 (LiFePO4) etc..Electronic equipment
The high powers of miniaturization and electric tool etc. propose new higher requirement to lithium ion battery.
LiFePO4 (LiFePO4) have that security performance is good, environmental pollution is little, the cheap and circulation longevity
The clear superiorities such as life is long, become miniaturized electronics, electric tool, electrokinetic cell and following large-scale energy storage
The preferred material of equipment.But, LiFePO4There is ion and electronic conductivity relatively low (about 10-9S/cm)、
The inherent shortcoming of discharge voltage plateau relatively low (about 3.3-3.4V) limits its wider application.In order to
Improve LiFePO4Discharge voltage plateau, by LiFePO4Part or all ferrum uses manganese to replace and obtains
Lithium ferric manganese phosphate (LiMnxFe1-xPO4, 0≤x≤1), manganese valence conversion can obtain the electric discharge of 4.1V
Voltage platform, but it is as the increase of Fe content, ion and the electronic conductivity of lithium ferric manganese phosphate become more
Low cause lithium ion deintercalation difficulty.People are by various methods (special carbon source, multi-element doping etc.) at present
Improve the electric conductivity of lithium ferric manganese phosphate, but be still difficult to obtain excellent chemical property.
Chinese patent application CN103762362A, CN103545522A, CN102810664A etc. are open
Employing hydro-thermal method or solvent structure lithium ferric manganese phosphate material, lithium ferric manganese phosphate material has once
Grain nanorize, degree of crystallinity advantages of higher thus relatively other synthetic methods preferably chemical property can be obtained.
But, the chemical property of lithium ferric manganese phosphate material improves the most limited, and problem main cause includes synthesis
The particle size homogeneity of product is not and the poor effect etc. of carbon cladding.
Therefore, prior art is necessary to improve further.
Summary of the invention
The technical problem to be solved is to provide the preparation method of a kind of positive electrode, and the method can
The positive electrode homogeneous to obtain nanoscale, granule-morphology, this positive electrode has good electric conductivity,
Excellent circulation and high rate performance.
The invention provides the preparation method of a kind of positive electrode, described preparation method comprises the following steps:
Lithium source is dissolved in the mixed solvent of deionized water and ethylene glycol and obtains the first solution, phosphorus source is dissolved in
Ethylene glycol obtains the second solution, by Organic substance, source of iron or/and manganese source is dissolved in deionized water and ethylene glycol
Mixed solvent in obtain the 3rd solution, wherein said lithium source, source of iron, manganese source, phosphorus source according to Li, Fe,
The amount of the material of Mn, P mixes than 3:1-x:x:1, wherein 0≤x≤1；Described second solution is added
Enter and obtain the first suspension in described first solution, described 3rd solution is joined described first and suspends
Liquid obtains the second suspension；Described second suspension is sealed in water heating kettle and carries out hydro-thermal reaction, institute
Stating second suspension compactedness in described water heating kettle is 50-90%, and hydrothermal temperature is 120-200 DEG C,
The hydro-thermal reaction time is 5-30h, and washings hot is dried to obtain described positive electrode.
Preferably, described preparation method also includes described positive electrode being carried out carbon cladding, including following step
Rapid: described positive electrode is mixed with carbon source, it is placed under inert atmosphere sintering, sintering temperature is 500-800 DEG C,
Sintering time is 2-20h, and described carbon source is 0.01-0.2 with the mass ratio of described positive electrode.
Preferably, described sintering temperature is 600-700 DEG C.
Preferably, described carbon source is 0.08-0.15 with the mass ratio of described positive electrode.
Preferably, described 3rd solution joins by the way of dropping and obtains the in described first suspension
Two suspensions.
Preferably, described Organic substance selected from vitamin E, carotenoid and derivant thereof, ascorbic acid,
At least one in ascorbyl palmitate, arabo-ascorbic acid.
Preferably, described Organic substance is 0.1-10 with the mass ratio of described positive electrode.
Preferably, in described mixed solvent, deionized water and ethylene glycol volume range are 0.01-0.19.
Preferably, described lithium source be in lithium dihydrogen phosphate, lithium acetate, lithium nitrate, Lithium hydrate at least
A kind of.
Preferably, source of iron is Ferrous acetate, iron acetate, ferrous nitrate, ferric nitrate, ferrous sulfate, sulfur
One in acid ferrum, ferrous chloride, iron chloride.
Preferably, at least one during phosphorus source is ammonium phosphate, ammonium dihydrogen phosphate, diammonium phosphate, phosphoric acid.
Preferably, described manganese source be protochloride manganese, oxalic acid Asia manganese, manganese sulfate, manganese nitrate, manganous oxide,
At least one in manganese acetate, manganese acetylacetonate, manganese sesquioxide managnic oxide.
Preferably, at least one during described carbon source is saccharide, oils and fats, organic acid, organic acid esters, alcohol.
Compared with prior art, this preparation method simple possible, applied widely, low cost, it is suitable for big
Technical scale metaplasia is produced.
The invention allows for a kind of positive electrode, described positive electrode is prepared by said method.
Compared with prior art, positive electrode prepared by the present invention is nanoscale, and granule-morphology is homogeneous, one
Cause is good.
The invention allows for a kind of battery, including positive pole, negative pole and electrolyte, described positive pole includes
State positive electrode.
Compared with prior art, the battery table that the present invention proposes reveals higher specific discharge capacity and excellence
Circulation, high rate performance.
Accompanying drawing explanation
Fig. 1 is positive electrode LiFePO in embodiment 1-44(a), positive electrode LiMn0.4Fe0.6PO4(b), just
Pole material LiMn0.8Fe0.2PO4(c) and positive electrode LiMnPO4The XRD figure of (d)；
Fig. 2 is positive electrode LiFePO in embodiment 1-44(a), positive electrode LiMn0.4Fe0.6PO4(b), just
Pole material LiMn0.8Fe0.2PO4(c) and positive electrode LiMnPO4The SEM figure of (d)；
Fig. 3 is battery high rate performance test curve in embodiment 5；
Fig. 4 is the relation curve of battery charging/discharging voltage under different electric currents and specific capacity in embodiment 5；
Fig. 5 is battery high rate performance test curve in embodiment 6；
Fig. 6 is the relation curve of battery charging/discharging voltage under different electric currents and specific capacity in embodiment 6；
Fig. 7 is battery high rate performance test curve in embodiment 7；
Fig. 8 is the relation curve of battery charging/discharging voltage under different electric currents and specific capacity in embodiment 7；
Fig. 9 is battery high rate performance test curve in embodiment 8；
Figure 10 is the relation curve of battery charging/discharging voltage under different electric currents and specific capacity in embodiment 8；
Figure 11 is battery high rate performance test curve in embodiment 9；
Figure 12 is the relation curve of battery charging/discharging voltage under different electric currents and specific capacity in embodiment 9；
Figure 13 is battery high rate performance test curve in embodiment 10；
Figure 14 is battery high rate performance test curve in embodiment 11.
Detailed description of the invention
In order to make technical problem solved by the invention, technical scheme and beneficial effect clearer,
Below in conjunction with embodiment, the present invention is further elaborated.Should be appreciated that described herein
Specific embodiment only in order to explain the present invention, is not intended to limit the present invention.
The present invention proposes the preparation method of a kind of positive electrode, and preparation method has steps of:
Lithium source is dissolved in the mixed solvent of deionized water and ethylene glycol and obtains the first solution, phosphorus source is molten
Solution obtains the second solution in ethylene glycol, by Organic substance, source of iron or/and manganese source is dissolved in deionized water and second
In the mixed solvent of glycol obtain the 3rd solution, wherein lithium source, source of iron, manganese source, phosphorus source according to Li, Fe,
The amount of the material of Mn, P mixes than 3:1-x:x:1, wherein 0≤x≤1；
Second solution is joined in the first solution and obtain the first suspension, the 3rd solution is joined first
Suspension obtains the second suspension；
Being sealed in water heating kettle by second suspension and carry out hydro-thermal reaction, the second suspension is in water heating kettle
Compactedness is 50-90%, and hydrothermal temperature is 120-200 DEG C, and the hydro-thermal reaction time is 5-30h, washes
Wash hydrothermal product, be dried to obtain positive electrode.
Preferably, preparation method also includes positive electrode is carried out carbon cladding, comprises the steps: just
Pole material mixes with carbon source, is placed under inert atmosphere sintering, and sintering temperature is 500-800 DEG C, during sintering
Between be 2-20h, the mass ratio of carbon source and positive electrode is 0.01-0.2.
The present invention uses ethylene glycol and deionized water mixed solvent, make lithium source, phosphorus source, source of iron and manganese source by
Configuring solution according to particular order, wherein deionized water plays the Solubility of Substances effect of raising source, and ethylene glycol rises
Dispersed effect is reached to improving solution viscosity；It is simultaneously introduced Organic substance in the solution, it is preferred that have
Machine thing is the Organic substance with non-oxidizability, on the one hand can maintain metal ion lower valency in the solution,
On the other hand make its carbonization under hydrothermal conditions, i.e. can be coated on its surface and obtain a carbon cladding,
Particle growth and reunion can be hindered again.It is furthermore preferred that again carbon source is physically or chemically mixed with positive electrode
Close and obtain secondary carbon cladding through high temperature cabonization.The positive electrode that the present invention obtains has the high rate performance of excellence
And cycle performance.The preparation method simple possible that the present invention provides, applied widely, low cost, it is suitable for
Large-scale industrial production
The preparation method of the present invention includes three kinds of situations: as x=0, the present invention is to provide a kind of positive pole
Material LiFePO4Preparation method；As 0 ＜ x ＜ 1, the present invention is to provide a kind of positive electrode containing manganese
The preparation method of the lithium ferric manganese phosphate material of doping；As x=1, the present invention is to provide a kind of positive pole material
Material LiMnPO4Preparation method.
From the description above, the present invention has three kinds of embodiments, will describe in detail respectively below.
Embodiment one
As x=0, the invention provides a kind of LiFePO4 (LiFePO4) preparation method, including
Following steps:
Lithium source is dissolved in the mixed solvent of deionized water and ethylene glycol and obtains the first solution, phosphorus source is molten
Solution obtains the second solution in ethylene glycol, and Organic substance and source of iron are dissolved in the mixed of deionized water and ethylene glycol
Obtaining the 3rd solution in bonding solvent, wherein lithium source, source of iron, phosphorus source are according to the amount of the material of Li, Fe, P
Mix than 3:1:1；Second solution is joined in the first solution and obtain the first suspension, then by the 3rd
Solution joins and obtains the second suspension in the first suspension；Second suspension is sealed in water heating kettle
Row hydro-thermal reaction, second suspension compactedness in water heating kettle is 50%-90%, and hydrothermal temperature is
120-200 DEG C, the hydro-thermal reaction time is 5-30h, and washings hot is dried to obtain positive electrode.
Preferably, preparation method also includes positive electrode is carried out carbon cladding, comprises the steps:
Being mixed with carbon source by positive electrode, be placed under inert atmosphere sintering, sintering temperature is 500-800 DEG C,
Sintering time is 2-20h, and carbon source is 0.01-0.2 with the mass ratio of positive electrode.
Preferably, Organic substance is the Organic substance with non-oxidizability, such as phenols, lipid, saccharide compound.
More preferably, Organic substance is selected from vitamin E, carotenoid and derivant thereof, ascorbic acid, anti-bad
At least one in hematic acid cetylate, arabo-ascorbic acid.
Organic quality is 0.1-10 with the mass ratio of positive electrode.Having non-oxidizability Organic substance can be steady
Determining the lower valency of iron ion, prevent the oxidation of iron ion, in water-heat process, Organic substance can be with carbonization bag simultaneously
Overlay on LiFePO4 surface, i.e. define a homogeneous carbon coating layer, hydrothermal product granule can be hindered
Growing up of size, it is thus achieved that the nano-grade lithium iron phosphate of a carbon cladding.
Concrete, lithium source is at least one in lithium dihydrogen phosphate, lithium acetate, lithium nitrate, Lithium hydrate,
Preferably, lithium source is Lithium hydrate.Molten less than in deionized water of lithium source dissolubility in ethylene glycol
Xie Du, the present invention uses mixed solvent to come dissolving lithium source, and wherein ethylene glycol plays raising solution viscosity and reaches
Dispersed effect, deionized water plays the Solubility of Substances effect of raising source, as such, it is possible to make lithium source fill
Divide, be dissolved in mixed solvent uniformly.
Phosphorus source is at least one in ammonium phosphate, ammonium dihydrogen phosphate, diammonium phosphate, phosphoric acid, it is preferable that
Phosphorus source is phosphoric acid.Phosphorus source is dissolved in ethylene glycol, it is therefore an objective to the second solution is being joined the first solution
Time middle, slow down the response speed of phosphorus source and lithium source, thus obtain uniform milk-white coloured suspension.Example,
Second solution joins in the first solution by the way of directly mixing；Preferably, the second solution is by dripping
The mode added joins in the first solution, as such, it is possible to form uniform first suspension.
Source of iron is Ferrous acetate, iron acetate, ferrous nitrate, ferric nitrate, ferrous sulfate, iron sulfate, chlorine
Change the one in ferrous iron, iron chloride, it is preferable that described source of iron is in ferrous sulfate or ferrous chloride
Kind.
Same, use the mixed solvent of deionized water and ethylene glycol to dissolve source of iron, ethylene glycol plays raising
Solution viscosity reaches dispersed effect, and deionized water plays the Solubility of Substances effect of raising source, so,
Source of iron can be made to be dissolved in mixed solvent fully, uniformly.
Preferably, in mixed solvent, deionized water and ethylene glycol volume ratio are 0.01-0.19.
Preferably, the 3rd solution joins by the way of dropping and obtains the second suspension in the first suspension；
More preferably, the 3rd solution is stirred by limit, limit joins in the first suspension by the way of dripping and obtains
Second suspension.The speed of dropping can be more than or equal to 2mL/min, it is preferred that the speed of dropping is
2-40mL/min, can obtain finely dispersed second suspension by the way of dropping, beneficially lithium source,
Source of iron, manganese source, phosphorus source are dispersed so that the positive electrode granule of final preparation is homogeneous.
Do not have conditional, can first the first solution be joined in water heating kettle, add the second solution and obtain
First suspension, adds the 3rd solution and obtains the second suspension, directly prepares second in water heating kettle and hangs
Then supernatant liquid carries out hydro-thermal reaction；Can also be that the container that other are clean obtains the second suspension, then will
Second suspension is transferred to water heating kettle and is carried out hydro-thermal reaction.
The length of hydro-thermal reaction time can directly affect the degree of crystallinity of hydrothermal product.The hydro-thermal reaction time is too short,
The degree of crystallinity of hydrothermal product is low, and the material granule little Yi of formation reunites, and hydro-thermal overlong time can cause not
Necessary energy waste.Preferably, the hydro-thermal reaction time is 5-30h.
Water heating kettle can be self-generated pressure formula counteracting tank, high-pressure digestion tank, pressure pan, reactor, pressure
Molten bullet, the one in hydrothermal synthesis reaction still, digester, Hydrothermal Synthesis still, experiment reactor.Logical
Cross the second suspension and the compactedness of water heating kettle and hydrothermal temperature can converse hydro-thermal reaction pressure,
Concrete, hydro-thermal reaction pressure is 3-20Mpa.
By hydrothermal product by deionized water centrifuge washing to remove foreign ion therein, after drying and get final product
To positive electrode.The mode being dried is not particularly limited, and can be to dry or give a constant temperature in atmosphere
Degree is such as 50-80 DEG C thus accelerates it and is dried.
Preferably, positive electrode carrying out secondary carbon cladding, carbon source is saccharide, oils and fats, organic acid, has
At least one in machine acid esters and alcohol.Alcohol includes small molecular alcohol or high molecular alcohol, such as polyvinyl alcohol (PVA)
With Polyethylene Glycol (PEG) etc..
The quality of carbon source and positive electrode is 0.01-0.2 than scope, it is preferable that the matter of carbon source and hydrothermal product
Amount ratio is 0.08-0.15.
Inert atmosphere is at least one in argon, nitrogen, helium, hydrogen, argon hydrogen gaseous mixture.
Sintering purpose is that sintering temperature can affect carbon in order to form second layer carbon coating layer on positive electrode
Source carbonizing degree, sintering temperature is too low, causes carbon source carbonizing degree low so that the electric conductivity of positive electrode
Bad, affect the capacity of positive electrode；And sintering temperature temperature is too high, positive electrode granule is caused to enter one
The big reunion of step-length.Preferably, sintering temperature is 600-700 DEG C.
This preparation method is simple, economy and facility, can prepare the positive pole material that nanoscale, granule-morphology are homogeneous
Material LiFePO4, positive electrode has good degree of crystallinity, excellent circulation and high rate performance.
Embodiment two
When 0 < x < when 1, the invention provides a kind of lithium ferric manganese phosphate (LiMnxFe1-xPO4) preparation side
Method, comprises the following steps:
Lithium source is dissolved in the mixed solvent of deionized water and ethylene glycol and obtains the first solution, phosphorus source is molten
Solution obtains the second solution in ethylene glycol, and Organic substance, source of iron and manganese source are dissolved in deionized water and second two
In the mixed solvent of alcohol obtain the 3rd solution, wherein lithium source, source of iron, manganese source, phosphorus source according to Li, Fe,
The amount of the material of Mn, P mixes than 3:1-x:x:1；Second solution is joined in the first solution and obtain
First suspension, then the 3rd solution is joined the first suspension obtains the second suspension；, hang second
Supernatant liquid seals in water heating kettle and carries out hydro-thermal reaction, and second suspension compactedness in water heating kettle is
50%-90%, hydrothermal temperature is 120-200 DEG C, and the hydro-thermal reaction time is 5-30h, washings delivery in hot weather
Thing, obtains positive electrode.
Preferably, preparation method also includes positive electrode is carried out carbon cladding, comprises the steps: just
Pole material mixes with carbon source, is placed under inert atmosphere sintering, and sintering temperature is 500-800 DEG C, during sintering
Between be 2-20h, the mass ratio of carbon source and positive electrode is 0.01-0.2.
Manganese source is protochloride manganese, oxalic acid Asia manganese, manganese sulfate, manganese nitrate, manganous oxide, manganese acetate, second
At least one in acyl acetone manganese, manganese sesquioxide managnic oxide, it is preferable that manganese source be manganese sulfate, protochloride manganese and
One in manganese acetate.
In the present invention, the span of x is 0 ＜ x ＜ 1, i.e. can use the method synthesis ferrimanganic arbitrary proportion
Lithium ferric manganese phosphate (LiMnxFe1-xPO4) positive electrode.Preferably, 0.4≤x≤0.8.
In a preferred embodiment, x=0.8, lithium source, manganese source, source of iron, phosphorus source according to Li, Mn,
The amount of the material of Fe, P mixes than 3:0.8:0.2:1, and obtained lithium ferric manganese phosphate material has logical
Formula LiMn0.8Fe0.2PO4。
In a more preferred embodiment, x=0.4, lithium source, manganese source, source of iron, phosphorus source according to Li, Mn,
The amount of the material of Fe, P mixes than 3:0.4:0.6:1, and obtained lithium ferric manganese phosphate material has logical
Formula LiMn0.4Fe0.6PO4。
In addition to features above, the further feature in embodiment two is with embodiment one, the most another
One repeats.
This preparation method is simple, economy and facility, can prepare the positive pole material that nanoscale, granule-morphology are homogeneous
Material LiMnxFe1-xPO4, positive electrode has good degree of crystallinity, excellent circulation and high rate performance.
Embodiment three
As x=1, the invention provides a kind of lithium manganese phosphate (LiMnPO4) preparation method, including
Following steps:
Lithium source is dissolved in the mixed solvent of deionized water and ethylene glycol and obtains the first solution, phosphorus source is molten
Solution obtains the second solution in ethylene glycol, and Organic substance and manganese source are dissolved in the mixed of deionized water and ethylene glycol
Obtaining the 3rd solution in bonding solvent, wherein lithium source, manganese source, phosphorus source are according to the amount of the material of Li, Fe, P
Mix than 3:1:1；
Second solution is joined in the first solution and obtain the first suspension, then the 3rd solution is joined
One suspension obtains the second suspension；
Being sealed in water heating kettle by second suspension and carry out hydro-thermal reaction, the second suspension is in water heating kettle
Compactedness is 50%-90%, and hydrothermal temperature is 120-200 DEG C, and the hydro-thermal reaction time is 5-30h, washes
Wash hydrothermal product, be dried to obtain positive electrode.
Preferably, preparation method also includes positive electrode is carried out carbon cladding, comprises the steps: just
Pole material mixes with carbon source, is placed under inert atmosphere sintering, and sintering temperature is 500-800 DEG C, during sintering
Between be 2-20h, the mass ratio of carbon source and positive electrode is 0.01-0.2.
Manganese source is protochloride manganese, oxalic acid Asia manganese, manganese sulfate, manganese nitrate, manganous oxide, manganese acetate, second
At least one in acyl acetone manganese, manganese sesquioxide managnic oxide, it is preferable that manganese source be manganese sulfate, protochloride manganese and
One in manganese acetate.
In addition to features above, the further feature in embodiment three is with embodiment one, the most another
One repeats.
This preparation method is simple, economy and facility, can prepare the positive pole material that nanoscale, granule-morphology are homogeneous
Material LiMnPO4, positive electrode has good degree of crystallinity, excellent circulation and high rate performance.
The invention allows for a kind of positive electrode, positive electrode has formula LiMnxFe1-xPO4, wherein
0≤x≤1, positive electrode is prepared by said method.
The invention allows for a kind of battery, including positive pole, negative pole, electrolyte, positive pole includes by above-mentioned
The positive electrode that method is prepared.The battery that the present invention provides has the high rate performance of excellence.
Below by embodiment, the present invention is further described.
Embodiment 1
Raw material: 3mmol Lithium hydrate, 1mmol ferrous sulfate, 1mmol phosphoric acid, 1mmol Vitamin C
Acid, 65mL ethylene glycol, 15mL deionized water.
3mmol Lithium hydrate is dissolved in the mixed solvent of 10mL deionized water and 25mL ethylene glycol and obtains
Obtain the first solution, 1mmol phosphoric acid is dissolved in 10mL ethylene glycol and obtains the second solution, by 1mmol
Ascorbic acid and 1mmol ferrous sulfate are dissolved in 5mL deionized water and the mixed solvent of 30mL ethylene glycol
Middle acquisition the 3rd solution.
Second solution is joined in the first solution and obtain the first suspension, then the 3rd solution is added dropwise over
The second suspension is obtained in the first suspension.
Put into the second suspension teflon-lined stainless steel cauldron seals and carry out hydro-thermal reaction,
Hydrothermal temperature is 180 DEG C, and the hydro-thermal reaction time is 10h.After hydro-thermal reaction terminates, by water in liner
It is dried after hot centrifuge washing, obtains positive electrode.
Being mixed with positive electrode by glucose, be placed under nitrogen atmosphere sintering, sintering temperature is 650 DEG C,
Sintering time is 8h, and glucose and positive electrode mass ratio are 0.08, obtains positive electrode carbon bag after cooling
The LiFePO covered4, it is designated as a.
Embodiment 2
Embodiment 2 with embodiment 1 except that, in raw material, 1mmol ferrous sulfate is changed to 0.4mmol
Manganese sulfate and 0.6mmol ferrous sulfate, remainder, with embodiment 1, obtains positive electrode carbon cladding
LiMn0.4Fe0.6PO4, it is designated as b.
Embodiment 3
Embodiment 3 with embodiment 1 except that, in raw material, 1mmol ferrous sulfate is changed to 0.8mmol
Manganese sulfate and 0.2mmol ferrous sulfate, remainder, with embodiment 1, obtains positive electrode carbon cladding
LiMn0.8Fe0.2PO4, it is designated as c.
Embodiment 4
Embodiment 4 with embodiment 1 except that, in raw material, 1mmol ferrous sulfate is changed to 1mmol
Manganese sulfate, remainder, with embodiment 1, obtains the LiMnPO of positive electrode carbon cladding4, it is designated as d.
Positive electrode performance test
Use X-ray diffraction (XRD) to observe the crystal structure of material, use scanning electron microscope (SEM)
Observe pattern and the grain diameter of positive electrode, use carbon coated in carbon and sulfur analytical instrument detection positive electrode
Content.
Fig. 1 is the XRD figure of positive electrode a, b, c, d in embodiment 1-4, it can be seen that
Positive electrode a (Fig. 1 a), positive electrode b (Fig. 1 b), positive electrode c (Fig. 1 c), positive electrode d
(Fig. 1 d) is pure phase.The result shows positive electrode that this preparation method obtains ferrimanganic for arbitrarily than
It is pure phase during example, and the degree of crystallinity of positive electrode is high.
Fig. 2 is the SEM figure of positive electrode a, b, c, d in embodiment 1-4, the result shows this
The positive electrode particle size size that preparation method obtains is about 100nm, and granule-morphology is homogeneous.
Embodiment 5
The preparation of battery
Battery types is button cell, and model is CR2032.
Electrolyte be 1mol/L lithium hexafluoro phosphate be solute, solvent be mass ratio be the ethylene of 1:1:1
Alkene ester, diethyl carbonate, dimethyl carbonate mixes.
Isolating membrane is celgard2400 thin polymer film.
Prepared by positive plate: by positive electrode LiFePO in embodiment 14, conductive agent acetylene black, binding agent
Kynoar is 80:1:1 mixing according to mass ratio, and wherein Kynoar is dissolved in N-methyl pyrrole
In pyrrolidone, mass fraction is 5%, is coated on aluminium foil after mix homogeneously, and thickness is 200 μm, 120 DEG C
After being dried 6 hours, make the positive plate of a diameter of Φ 14mm.Positive plate active substance load capacity is 3.0mg
Left and right.
Negative plate selects pure metal lithium sheet.
Battery assembles: the glove box under argon shield.
Embodiment 6
LiMn during cell positive material uses embodiment 2 in embodiment 60.4Fe0.6PO4, remaining structure of battery
Become and assembling mode is with embodiment 5.
Embodiment 7
Cell positive material and positive electrode LiMn in embodiment 2 in embodiment 70.4Fe0.6PO4Distinguish
Sintering temperature in glucose and hydrothermal product is 600 DEG C, and positive electrode remainder is with embodiment 2.Electricity
Remaining composition of pond and assembling mode are with embodiment 5.
Embodiment 8
Cell positive material and positive electrode LiMn in embodiment 2 in embodiment 80.4Fe0.6PO4Distinguish
Sintering temperature in glucose and hydrothermal product is 700 DEG C, and positive electrode remainder is with embodiment 2.Electricity
Remaining composition of pond and assembling mode are with embodiment 5.
Embodiment 9
Cell positive material and positive electrode LiMn in embodiment 2 in embodiment 90.4Fe0.6PO4Distinguish
Mass ratio in glucose Yu hydrothermal product is 0.15, and positive electrode remainder is with embodiment 2.Battery
Remaining is constituted and assembling mode is with embodiment 5.
Embodiment 10
LiMn during positive electrode uses embodiment 3 in embodiment 100.8Fe0.2PO4, battery remaining constitute and
Assembling mode is with embodiment 5.
Embodiment 11
LiMnPO during positive electrode uses embodiment 4 in embodiment 114, remaining composition of battery and assembling
Mode is with embodiment 5.
The battery assembled in embodiment 5-11 is carried out charge-discharge performance test, and test voltage is interval: phosphoric acid
Ferrum lithium selects 2.2-4.0V, lithium ferric manganese phosphate and lithium manganese phosphate to select 2.2-4.5V.Test electric current:
1C=160mA/g, battery testing temperature: 25 ± 2 DEG C.
Table 1 is the carbon content of positive electrode in embodiment 1-4 and embodiment 9, and this result shows this system
The positive electrode that Preparation Method obtains all is coated with appropriate carbon content, so, both can improve positive electrode
Electric conductivity, do not interfere with again the specific capacity of positive electrode.
Table 1
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 9 | |
| Carbon content | 1.84wt% | 2.11wt% | 1.82wt% | 2.02wt% | 3.87wt% |
Fig. 3 is battery high rate performance test curve in embodiment 5；Fig. 4 be in embodiment 5 battery not
Relation curve with the charging/discharging voltage under electric current Yu specific capacity；Table 2 be in embodiment 5 battery in difference
Specific discharge capacity under multiplying power and electric discharge mean voltage.
Table 2
| Multiplying power (C) | 0.1 | 1 | 2 | 5 | 10 | 15 | 20 |
| Specific discharge capacity (mAh/g) | 155 | 150 | 148 | 144 | 140 | 137 | 133 |
| Electric discharge mean voltage (V) | 3.418 | 3.395 | 3.373 | 3.322 | 3.254 | 3.183 | 3.124 |
Table 3 is battery specific discharge capacity under different multiplying in embodiment 6-8.
Table 3
From table 2 with table 3 data it can be seen that embodiment 6 battery there is relative preferably high rate performance,
The most as can be seen from Figure 5: battery is when the multiplying power discharging to be stepped up, and discharge capacity of the cell is decayed
The slowest, and battery discharge with 20C after recover to discharge with little multiplying power 0.5C, discharge capacity of the cell
Almost consistent with the discharge capacity of 0.5C circulation with the 3-10 time before, illustrate that battery has good following
Ring and high rate performance.
It addition, data all show in Fig. 7, Fig. 9, Figure 11 and Figure 13: the present invention provide battery with
After big multiplying power (20C) electric discharge, then recovering to discharge with little multiplying power (0.5C), discharge capacity of the cell is equal
Level before can returning to, illustrates that battery has good circulation and high rate performance.
The foregoing is only presently preferred embodiments of the present invention, not in order to limit the present invention, all at this
Any amendment, equivalent and the improvement etc. made within the spirit of invention and principle, should be included in this
Within the protection domain of invention.
Claims (15)
1. the preparation method of a positive electrode, it is characterised in that described preparation method comprises the following steps:
Lithium source is dissolved in the mixed solvent of deionized water and ethylene glycol and obtains the first solution, phosphorus source is dissolved
The second solution is obtained, by Organic substance, source of iron or/and manganese source is dissolved in deionized water and second in ethylene glycol
In the mixed solvent of glycol obtain the 3rd solution, wherein said lithium source, source of iron, manganese source, phosphorus source according to
The amount of the material of Li, Fe, Mn, P mixes than 3:1-x:x:1, wherein 0≤x≤1；
Described second solution is joined in described first solution and obtains the first suspension, by described 3rd solution
Join in described first suspension and obtain the second suspension；
Being sealed in water heating kettle by described second suspension and carry out hydro-thermal reaction, described second suspension is described
Compactedness in water heating kettle is 50-90%, and hydrothermal temperature is 120-200 DEG C, the hydro-thermal reaction time
For 5-30h, washings hot, it is dried to obtain described positive electrode.
Preparation method the most according to claim 1, it is characterised in that: described preparation method also includes institute
State positive electrode and carry out carbon cladding, comprise the following steps:
Being mixed with carbon source by described positive electrode, be placed under inert atmosphere sintering, sintering temperature is 500-800 DEG C,
Sintering time is 2-20h, and described carbon source is 0.01-0.2 with the mass ratio of described positive electrode.
Preparation method the most according to claim 2, it is characterised in that: described sintering temperature is 600-700 DEG C.
Preparation method the most according to claim 2, it is characterised in that: described carbon source and described positive electrode
Mass ratio be 0.08-0.15.
Preparation method the most according to claim 1, it is characterised in that: described 3rd solution is by dropping
Mode joins in described first suspension and obtains the second suspension.
Preparation method the most according to claim 1, it is characterised in that: described Organic substance selected from vitamin E,
In carotenoid and derivant, ascorbic acid, ascorbyl palmitate, arabo-ascorbic acid
At least one.
Preparation method the most according to claim 1, it is characterised in that: described Organic substance and described positive pole material
The mass ratio of material is 0.1-10.
Preparation method the most according to claim 1, it is characterised in that: deionized water in described mixed solvent
It is 0.01-0.19 with ethylene glycol volume range.
Preparation method the most according to claim 1, it is characterised in that: described lithium source be lithium dihydrogen phosphate,
At least one in lithium acetate, lithium nitrate, Lithium hydrate.
Preparation method the most according to claim 1, it is characterised in that: source of iron be Ferrous acetate, iron acetate,
One in ferrous nitrate, ferric nitrate, ferrous sulfate, iron sulfate, ferrous chloride, iron chloride.
11. preparation methoies according to claim 1, it is characterised in that: phosphorus source is ammonium phosphate, biphosphate
At least one in ammonium, diammonium phosphate, phosphoric acid.
12. preparation methoies according to claim 1, it is characterised in that: described manganese source is protochloride manganese, grass
Acid sub-manganese, manganese sulfate, manganese nitrate, manganous oxide, manganese acetate, manganese acetylacetonate, manganese sesquioxide managnic oxide
In at least one.
13. preparation methoies according to claim 1, it is characterised in that: described carbon source be saccharide, oils and fats,
At least one in organic acid, organic acid esters, alcohol.
14. 1 kinds of positive electrodes, described positive electrode is prepared by the either method in claim 1-13.
15. 1 kinds of batteries, including positive pole, negative pole and electrolyte, described positive pole includes as claimed in claim 14
Positive electrode.
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