CN107665983A - Anode material for lithium-ion batteries and preparation method thereof and lithium ion battery - Google Patents
Anode material for lithium-ion batteries and preparation method thereof and lithium ion battery Download PDFInfo
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
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- C01B25/16—Oxyacids of phosphorus; Salts thereof
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- C01B25/375—Phosphates of heavy metals of iron
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- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
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Abstract
The invention provides a kind of anode material for lithium-ion batteries, anode material for lithium-ion batteries, it is characterized in that, the anode material for lithium-ion batteries includes nickle cobalt lithium manganate and is arranged on the clad on the nickle cobalt lithium manganate surface, wherein, the material of the clad is phosphoric acid ferrovanadium lithium or vanadyl phosphate lithium.The voltage platform of coating layer material and nickle cobalt lithium manganate approaches, and can improve security, the cycle performance of nickel-cobalt-manganese ternary material well, moreover it is possible to keeps higher energy density.Present invention also offers the preparation method of anode material for lithium-ion batteries and lithium ion battery.
Description
Technical field
The present invention relates to field of lithium ion battery, and in particular to a kind of anode active material of lithium ion battery and its preparation side
Method and lithium ion battery.
Background technology
Lithium ion battery is the green high-capacity battery of a new generation, and important function is increasingly shown in every field.As lithium
The important component of ion battery, the positive electrode of lithium battery decide the performance of lithium battery, price and development.Nickel cobalt manganese three
First positive electrode is Olivine-type Cathode Material in Li-ion Batteries, it has, and energy density is high, voltage platform is high, crystal structure is preferable,
The advantages that self discharge is small, memory-less effect, but the heat endurance of the material is bad, security is poor, under high charge blanking voltage
Cycle performance nor highly desirable.
In order to solve the security of nickel-cobalt-manganternary ternary anode material and cycle performance, generally use ferric phosphate in the prior art
The materials such as lithium carry out coating modification to it, to reduce deintercalation of the lithium ion in charge and discharge process to nickel-cobalt lithium manganate material
The influence of crystal structure, but the electronic conductivity of LiFePO4 is poor, and voltage platform is also much lower compared with nickel-cobalt-manganese ternary material,
The cycle performance and security performance of the positive electrode of modified gained are not improved well.
The content of the invention
To solve the above problems, the invention provides a kind of anode material for lithium-ion batteries, the lithium ion cell positive is lived
Property material be use with the voltage platform of nickel-cobalt-manganese ternary material similar in material (phosphoric acid ferrovanadium lithium or vanadyl phosphate lithium) make
For clad, surface modification is carried out to nickel-cobalt-manganese ternary material, can improve well nickel-cobalt-manganese ternary material security,
Cycle performance, moreover it is possible to keep higher energy density., should present invention also offers the preparation method of anode material for lithium-ion batteries
Preparation method is unique, effective, and coating layer material can be evenly coated to nickel-cobalt-manganese ternary material surface.
Specifically, first aspect present invention provides a kind of anode material for lithium-ion batteries, the lithium ion cell positive
Material includes nickle cobalt lithium manganate and is arranged on the clad on the nickle cobalt lithium manganate surface, wherein, the material of the clad is
Phosphoric acid ferrovanadium lithium or vanadyl phosphate lithium.
Wherein, the voltage platform of the nickle cobalt lithium manganate is 3.6-3.8V." voltage platform " refers to that battery exists in the application
During constant current charge-discharge, cell voltage has a stable process (hardly change or vary less), and this stationary value is just
It is charge and discharge platform；The stationary process occupies the overwhelming majority of whole charge or discharge time.
Wherein, the voltage platform of the phosphoric acid ferrovanadium lithium is 3.6-3.7V；The voltage platform of the vanadyl phosphate lithium is
3.8-3.9V。
The discharge and recharge scope of general nickle cobalt lithium manganate tertiary cathode material is 4.3-2.7V, and phosphoric acid ferrovanadium lithium is 4.3-
2.6V, vanadyl phosphate lithium are 4.2-2.8V, the present invention in use with the voltage platform of cobalt nickel lithium manganate ternary material similar in material
Material (phosphoric acid ferrovanadium lithium or vanadyl phosphate lithium) is used as clad, so can be avoided and is far below nickel cobalt manganese using voltage platform
When the material (such as LiFePO4, discharge and recharge scope are 3.8-2.0V) of sour lithium is to coat, in too high charging voltage to clad
LiFePO4 causes to overcharge, the problem of in too low discharge voltage and causing to put to matrix nickel-cobalt-manganese ternary material, Jin Erti
The security of high gained anode material for lithium-ion batteries, cycle performance, moreover it is possible to keep higher energy density.
Wherein, the thickness of the clad is 200-700nm.Such as can be 300,400,450,500 or 600nm.
Wherein, the mass ratio of the material of the clad and the nickle cobalt lithium manganate is (5-15)：(85-95), i.e., 1：
(5.7-19).Preferably 1：(8-19).More preferably 1：(15-19).Appropriate mass than coating layer material and nickel cobalt manganese
Sour lithium, guarantee can be made to form constitutionally stable clad type positive electrode, and make the positive electrode have preferable stability and
Preferable chemical property, in addition, also the capacity of positive electrode can be adjusted by adjusting the mass ratio.
Wherein, the coating layer material is discontinuous (i.e., discontinuously) is attached to the nickle cobalt lithium manganate surface.Further
Ground, the area of the clad cladding account for the 85-95% of the nickle cobalt lithium manganate total surface area.
Wherein, the nickle cobalt lithium manganate is spherical that its chemical formula is LiNixCoyMn1-x-yO2, x, y represent molar percentage,
0<X, y<1.Preferably, x span is 0.4-0.6.
Further, the particle diameter of nickle cobalt lithium manganate is 9-15 μm.
Wherein, the chemical formula of the phosphoric acid ferrovanadium lithium is LiFeaVbPO4(being abbreviated as LFVP), a, b represent molar percentage,
The ＜ b ＜ 2/3 of 0 ＜ a ＜ 1,0, and 2a+3b=2；Fe chemical valence is+divalent, and V chemical valence is+trivalent.
When coating layer material is phosphoric acid ferrovanadium lithium, the particle diameter of the anode material for lithium-ion batteries is micron order, preferably
For 10-30 μm.The compacted density of the anode material for lithium-ion batteries is 3.5-3.7g/cm3.Due to the lithium-ion electric of the present invention
The capacity and compacted density of pond positive electrode active materials are higher, are more beneficial for improving the energy density of battery, so as to expand the material
The application field of the battery of preparation.
When coating layer material is vanadyl phosphate lithium (LiVOPO4), the particle diameter of the anode material for lithium-ion batteries is micro-
Meter level, preferably 1 μm -1000 μm.The compacted density of the anode material for lithium-ion batteries is 3.5-3.7g/cm3。
The anode material for lithium-ion batteries that first aspect present invention provides, due to using the voltage with nickel-cobalt-manganese ternary material
The clad of phosphoric acid ferrovanadium lithium or vanadyl phosphate lithium as nickel-cobalt-manganese ternary material similar in platform, compared to using voltage platform
Relatively low LiFePO 4 material, clad is caused when the voltage range of coating layer material and ternary material can be avoided to mismatch
Overcharge and crossed to caused by the ternary material being wrapped by and put problem, the stability of gained positive electrode is good, degree of safety is high, circulation
Performance is also preferable, moreover it is possible to keeps higher energy density.
Second aspect of the present invention provides a kind of preparation method of anode material for lithium-ion batteries, comprises the following steps：
Coating layer material is provided, the coating layer material is phosphoric acid ferrovanadium lithium or vanadyl phosphate lithium；
The first solvent and film forming agent are added into the coating layer material, after being well mixed, obtains point of coating layer material
Dispersion liquid, add nickle cobalt lithium manganate and carry out mixing 0.5-4h, by gained mixture after 90-160 DEG C of vacuum drying, to drying institute
Obtain solids to sieve with 300-400 mesh, obtain anode material for lithium-ion batteries, the anode material for lithium-ion batteries includes nickel cobalt
LiMn2O4 and the clad for being arranged on the nickle cobalt lithium manganate surface；The film forming agent includes polyvinyl alcohol, polyethylene glycol, poly- dimension
At least one of ketone, neopelex and stearic acid.
Wherein, the mass ratio of the coating layer material and the nickle cobalt lithium manganate is (5-15)：(85-95), i.e., 1：(5.7-
19).Preferably 1：(8-19).More preferably 1：(15-19).
In the application, the film forming agent has certain viscosity, is also equipped with Action of Surfactant, contributes to nickel cobalt manganese three
First material adsorbs coating layer material, and nickel-cobalt-manganese ternary material, by mixing, can make bag in the dispersion liquid of coating layer material
Clad material is uniformly coated on nickel-cobalt-manganese ternary material surface.
Preferably, when the coating layer material is vanadyl phosphate lithium, also contain in the dispersion liquid of the coating layer material
Electrically conducting adhesive, the electrically conducting adhesive are super p (carbon black), Ketjen black, acetylene black, carbon nano-fiber (such as vapor phase growth
Carbon fibe (Vapor-grown carbon fiber, VGCF)), in one or more.The electrically conducting adhesive can improve phosphorus
The electric conductivity of sour vanadyl lithium.
Preferably, when the dispersion liquid of the coating layer material and nickle cobalt lithium manganate mix, mixing speed be 200~
500rpm。
Wherein, first solvent is included in 1-METHYLPYRROLIDONE, dimethyl sulfoxide (DMSO), acetone, water and ethanol at least
It is a kind of.First solvent can be selected according to the film forming agent of selection, the film forming agent is fully dissolved as far as possible.
Preferably, before being dried in vacuo to the gained mixture, in addition to：To gained mixture with 1000~
3000rpm is centrifuged 20~60 minutes, removes supernatant, collects precipitation.Vacuum drying afterwards is heavy for gained after centrifugation
Form sediment and carry out.
Wherein, the preparation process of the coating layer material is as follows：Coating layer material presoma is provided, in protective gas
Under, by the coating layer material presoma in 200-400 DEG C of constant temperature pre-burning 2-4h, then by the coating layer material forerunner after pre-burning
Body carries out ball milling, then the coating layer material presoma after ball milling is sintered；Wherein, the detailed process of the sintering is：First
150-250 DEG C, an Isothermal sinter 1-2h is warming up to, then is heated up at 550-700 DEG C, secondary Isothermal sinter 6-12h.
Wherein, when the coating layer material presoma is phosphoric acid ferrovanadium lithium presoma, the sintering is in protective gas
Lower progress；When the coating layer material presoma is vanadyl phosphate lithium presoma, the sintering is or oxygen in atmosphere
With being carried out under the mixed atmosphere of protective gas.
Further, in the sintering process, the heating rate for being warming up to 150-250 DEG C is 1-5 DEG C/min；From described one
The temperature (i.e. 150-250 DEG C) of secondary Isothermal sinter is warming up to the heating speed of the temperature (550-700 DEG C) of the secondary Isothermal sinter
Rate is 1-3 DEG C/min.
In the present invention, pre-burning is first carried out under protective gas to the coating layer material presoma, both may be used by pre-burning
To remove the impurity (such as excess complexing agent, reducing agent) in the coating layer material presoma, coating layer material is additionally aided
Lattice portion is formed in presoma, now forms semi-finished product；Then will enter again after the coating layer material presoma ball milling after pre-burning
Row multi-steps sintering, the temperature so sintered without Tai Gao and sintering time without it is oversize can be abundant by coating layer material presoma
Sintering, in addition, multi-steps sintering is more conducive to improve the lattice wellness of coating layer material；The ball milling of multi-steps sintering helps to refine
Coating layer material granular precursor, non-uniform components, increase activity are grown up with more preferable forming core, avoid the grain nucleation of coating layer material
Rate is poor, and yields is low.
Wherein, protective gas is at least one of nitrogen, argon gas and helium.Pre-burning is carried out in protective gas.
Pre-burning can prevent the ferrous ions in phosphoric acid vanadium iron lithium in protective gas.
Wherein, the particle diameter of gained coating layer material presoma is 100-300nm after ball milling.
In the present invention, the preparation method of the coating layer material presoma can be existing conventional method, such as high temperature solid-state
Reducing process, sol-gel process, spray drying process, hydro-thermal method or microwave method.
In an embodiment of the present invention, when the coating layer material is phosphoric acid ferrovanadium lithium, before the phosphoric acid ferrovanadium lithium
The preparation process for driving body is as follows：By lithium source, vanadium source, source of iron, phosphorus source Li in molar ratio：Fe：V：P=1：a：b：1 is weighed, and is added
Enter the second solvent, complexing agent and/or reducing agent, obtain mixed slurry after mixing is scattered, the pH for adjusting the mixed slurry is 1-
7, gained mixed slurry is dried in vacuo at 90-160 DEG C, obtains phosphoric acid ferrovanadium lithium (LFVP) presoma；Wherein, 0 ＜ a
The ＜ b ＜ 2/3 of ＜ 1,0, and 2a+3b=2.
Preferably, the forming process of the mixed slurry is as follows：Add solvent into the vanadium source, complexing agent and/or also
Former agent is dissolved, and obtains vanadium source solution；The lithium source, source of iron, phosphorus source are mixed with solvent, and the vanadium source for adding dissolving is molten
Liquid, obtain the mixed slurry.
Wherein, the lithium source be selected from lithium hydroxide, lithium chloride, lithium nitrate, lithium oxalate, lithium acetate, lithium carbonate, etc., phosphoric acid
At least one of lithium, lithium dihydrogen phosphate and the lithium of phosphoric acid hydrogen two；The vanadium source is selected from vanadic anhydride (V2O5), ammonium metavanadate
(NH4VO3At least one of)；The source of iron is selected from least one of ferrous nitrate, ferrous oxalate, frerrous chloride；The phosphorus
Source is selected from least one of ammonium dihydrogen phosphate, monoammonium phosphate, ammonium phosphate and phosphoric acid；The complexing agent is selected from citric acid, resisted
At least one of bad hematic acid, oxalic acid, tartaric acid, EDTA (ethylenediamine tetra-acetic acid), complex acid potassium and thiocarbamide；The second solvent choosing
From at least one of water, ethanol, ethylene glycol, propyl alcohol, isopropanol, isobutanol, methanol, n-butanol.
In another embodiment of the present invention, when the coating layer material is vanadyl phosphate lithium, the vanadyl phosphate lithium
The preparation process of presoma is as follows：By lithium source, vanadium source, phosphorus source Li in molar ratio：Fe：V：P=1：a：b：1 is mixed, and is added
Second solvent, complexing agent and/or reducing agent, the stirring in water bath at 65-100 DEG C, obtain mixed slurry, by gained mixed slurry in
It is dried in vacuo at 90-160 DEG C, obtains vanadyl phosphate lithium presoma.
Wherein, the complexing agent is in citric acid, ascorbic acid, oxalic acid, tartaric acid, EDTA, complex acid potassium and thiocarbamide
It is at least one；The reducing agent in citric acid, oxalic acid, sucrose, glucose, sodium sulfite and sodium thiosulfate at least one
Kind.Further, the complexing agent and reducing agent can be same material, such as be citric acid or oxalic acid.
Second aspect of the present invention provide anode material for lithium-ion batteries preparation method, by coating layer material, film forming agent,
Solvent is mixed with nickle cobalt lithium manganate, after vacuum drying, obtains the nickel-cobalt lithium manganate cathode material of clad cladding, the preparation
Method is unique, effective, and coating layer material can be evenly coated to nickel-cobalt-manganese ternary material surface, gained lithium ion cell positive material
Material has preferable structural stability, security and cycle performance.
Third aspect present invention provides a kind of preparation method of anode material for lithium-ion batteries, comprises the following steps：
Coating layer material presoma is provided, the coating layer material presoma is phosphoric acid ferrovanadium lithium presoma or vanadyl phosphate
Lithium presoma；In protective gas, constant temperature pre-burning 2-4h, cooling at 200-400 DEG C by the coating layer material presoma
Afterwards, the coating layer material presoma after pre-burning is obtained；
Coating layer material presoma after the pre-burning is dissolved in water soluble polar solvent, adds nickel cobalt mangaic acid thereto
Lithium carries out mixing 0.5-10h, obtains the first slurry, and first slurry is dried in vacuo in 90-160 DEG C, obtains positive pole
Material precursor；
The positive electrode material precursor is sintered, the detailed process of the sintering is：150-250 DEG C is first warming up to,
Isothermal sinter 1-2h, then heat up at 550-700 DEG C, secondary Isothermal sinter 6-12h；After cooling, to sintering gained solids
Sieved with 300-400 mesh, obtain anode material for lithium-ion batteries, the anode material for lithium-ion batteries include nickle cobalt lithium manganate and
It is arranged on the clad on the nickle cobalt lithium manganate surface.
Wherein, when containing phosphoric acid ferrovanadium lithium presoma in the positive electrode material precursor, the sintering is in protection gas
Carried out under body；When phosphoric acid vanadyl lithium presoma in the positive electrode material precursor, the sintering is or oxygen in atmosphere
Carried out under the mixed atmosphere of gas and protective gas.
Wherein, the mass ratio of the coating layer material presoma after the pre-burning and nickle cobalt lithium manganate is (5-15)：(85-
95), i.e., 1：(5.7-19).
Wherein, the water soluble polar solvent be selected from water, ethanol, ethylene glycol, 1-METHYLPYRROLIDONE, dimethyl sulfoxide (DMSO) and
One or more in acetone.
Wherein, the protective gas is at least one of nitrogen, argon gas and helium.
Wherein, method coating layer material presoma, the nickle cobalt lithium manganate after pre-burning mixed can be stirring, ultrasound,
Ball milling, sand milling or scattered at a high speed, it is only necessary to which they are well mixed, and concrete mode is not particularly limited.
In the present invention, pre-burning is first carried out under protective atmosphere to coating layer material presoma, can aid in by pre-burning
Lattice portion is formed in coating layer material presoma, now forms semi-finished product；Then by the coating layer material presoma after pre-burning
Continue multi-steps sintering after being mixed with lithium nickel cobalt dioxide, the temperature so sintered is without Tai Gao and sintering time is without oversize
Coating layer material presoma, lithium nickel cobalt dioxide are fully sintered, uniform clad can be sufficiently formed on lithium nickel cobalt dioxide surface；This
Outside, multi-steps sintering is more conducive to improve the lattice wellness of coating layer material.
The preparation method for the anode material for lithium-ion batteries that third aspect present invention provides, by the coating layer material of pre-sintering
Presoma first mixes cladding with lithium nickel cobalt dioxide, then the positive electrode material precursor to obtaining is sintered, and obtains clad cladding
Nickel-cobalt lithium manganate cathode material, the preparation method is unique, effective, and coating layer material can be evenly coated to nickel-cobalt-manganese ternary material
Surface, gained anode material for lithium-ion batteries have preferable structural stability, security and cycle performance.
The present invention sintering overall process carried out all in constant temperature oven, in sintering process it is any can under atmosphere protection uniformly
The Equipment for Heating Processing of heating can be used, such as vacuum drying oven, batch-type furnace, continuous tunnel furnace, rotary atmosphere furnace, clock hood type furnace, tube furnace, shuttle
Formula stove or pushed bat kiln etc..
Fourth aspect present invention provides a kind of lithium ion battery, and the lithium ion battery provides comprising first aspect present invention
Anode material for lithium-ion batteries.
Wherein, the lithium ion battery includes anode pole piece, cathode pole piece, barrier film, electrolyte and shell, wherein, positive pole
Anode material for lithium-ion batteries, conductive agent and the binding agent that pole piece is provided by collector, first aspect present invention form.
In embodiment of the present invention, the collector is aluminium foil, nickel screen or aluminum-plastic composite membrane.
In embodiment of the present invention, the conductive agent is acetylene black.
In embodiment of the present invention, the binding agent is Kynoar (PVDF), butadiene-styrene rubber newborn (SBR) or carboxymethyl
Sodium cellulosate (CMC).
The selection of cathode pole piece, barrier film, electrolyte and shell is industry prior art, does not do particular determination herein.
The lithium ion battery that fourth aspect present invention provides has higher energy density, cycle performance and security.
The advantages of embodiment of the present invention, will partly illustrate in the following description, a part according to specification be it is aobvious and
It is clear to, or can be known by the implementation of the embodiment of the present invention.
Brief description of the drawings
Fig. 1 is that the SEM (SEM) of the phosphoric acid ferrovanadium lithium presoma after pre-burning in the embodiment of the present invention 1 is shone
Piece；
Fig. 2 is the SEM photograph of phosphoric acid ferrovanadium lithium finished product made from the embodiment of the present invention 1；
Fig. 3 is the SEM photograph of nickle cobalt lithium manganate used in the embodiment of the present invention 1；
Fig. 4 is the SEM photograph of anode material for lithium-ion batteries made from the embodiment of the present invention 1；
Fig. 5 is XRD (X-ray diffraction) figure of anode material for lithium-ion batteries made from the embodiment of the present invention 1；
Fig. 6 is the DSC curve using button cell made of 1-3 of the embodiment of the present invention and comparative example 1-3 positive electrode.
Embodiment
As described below is the preferred embodiment of the present invention, it is noted that for those skilled in the art
For, under the premise without departing from the principles of the invention, some improvements and modifications can also be made, these improvements and modifications are also considered as
Protection scope of the present invention.
Embodiment 1：
A kind of preparation method of anode material for lithium-ion batteries, comprises the following steps：
(1) phosphoric acid ferrovanadium lithium presoma is prepared
Vanadic anhydride 0.55g is weighed, oxalic acid 9g adds 12mL deionized waters, and is heated to 60 DEG C, is sufficiently stirred to incite somebody to action
Dissolution of raw material, obtain vanadium source solution；Lithium carbonate 7.46g, ferric nitrate 79.17g, ammonium dihydrogen phosphate 23.24g are weighed, is dissolved in 45mL
After nitric acid, the vanadium source solution dissolved is added, after stirring 1h, obtains mixed slurry；Gained mixed slurry is carried out at 150 DEG C
Vacuum drying, obtains phosphoric acid ferrovanadium lithium (LFVP) presoma.
(2) pre-burning of LFVP presomas：By dried LFVP precursor powders under nitrogen atmosphere protection, with 5 DEG C/minute
The speed of clock is warming up to 300 DEG C, is incubated 2h, obtains the LFVP precursor powders after pre-burning.
(3) LFVP finished products are prepared：Into the LFVP presomas after above-mentioned pre-burning with ball powder ratio 10:1 adds agate bead, with agate
Nao grinding pots carry out ball milling refinement 300rpm/2h to precursor powder, and the particle diameter of the LFVP presomas after ball milling is about 200nm.
By the LFVP precursor powders after refinement, multi-steps sintering, elder generation are warming up to 2 DEG C/min speed under nitrogen protection
200 DEG C, Isothermal sinter 2h, then heated up with 2 DEG C/min speed at 700 DEG C, Isothermal sinter 8h, after furnace cooling, obtain phosphoric acid
Ferrovanadium lithium (LFVP) finished product.
(4) prepared by ternary raw material/phosphoric acid ferrovanadium lithium composite positive pole：
6.4g gained phosphoric acid ferrovanadium lithium is added in 100g 1-METHYLPYRROLIDONEs, and adds 1.5g polyvinyl alcohol
Stirring and dissolving 0.5h, obtain the dispersion liquid of coating layer material；
Weigh 100g nickel-cobalt-manganese ternary material Li (Ni0.5Co0.2Mn0.3)O2(average grain diameter is 14.5 μm), is added to
State after continuing to stir 1.5h in the dispersion liquid of coating layer material, 0.5h is centrifuged with 1000rpm rotating speeds, removes supernatant, it is heavy to collect
Form sediment, gained is deposited at 120 DEG C and is dried in vacuo 1h, obtain the nickel of the positive electrode of clad structure, i.e. phosphoric acid ferrovanadium lithium cladding
Cobalt manganic acid lithium.
The preparation method of lithium ion battery
By 800 grams of obtained anode material for lithium-ion batteries, 100 grams of conductive agent acetylene black, 100g according to the method described above
Binding agent Kynoar (PVDF), be added in 800g 1-METHYLPYRROLIDONE solution (nmp solution), be stirred under vacuum
2h is stirred in machine, anode sizing agent is made；Slurry is uniformly coated on aluminium foil, be subsequently placed in vacuum drying chamber 120 DEG C it is dry
Dry 12h, then diameter 14mm disk is punched into as positive pole.By positive plate, negative plate (diameter 14.5mm metal lithium sheet), every
Film (microporous polypropylene membranes of Celgard 2400) and electrolyte (1mo1/L LiPF6/ EC+DMC (volume ratios 1:1)) full of hydrogen
CR2025 type button cells are assembled into the glove box of gas, electrochemical property test will be carried out after battery standing 12h.Carry out electrification
When learning performance test, 25 DEG C of constant temperature are kept, using metal Li as to electrode, charging/discharging voltage scope 2.7-4.3V, 25 DEG C of constant temperature.
Detect following 3 detection projects of battery：
(a) 0.2C specific discharge capacities (mAh/g) first：In the case where charge and discharge voltage is 4.3-2.7V, filled with 0.2C current densities
Electric discharge；
(b) 1C circulates 100 capability retentions (%)：It is 4.3-2.7V in charge and discharge voltage, 1C current densities circulate 100
It is secondary；
(c) 1C mean voltages 4.3-2.7V, mean voltage when 1C discharges first；
Fig. 1, Fig. 2 are respectively the scanning of phosphoric acid ferrovanadium lithium (LFVP) presoma, LFVP finished products after pre-burning in the present embodiment 1
Electron microscope (SEM) photo, Fig. 3 are the SEM photograph of nickle cobalt lithium manganate used in the present embodiment 1；Fig. 4 is in the present embodiment 1
The SEM photograph of gained anode material for lithium-ion batteries；
As can be seen from Figure 1, by pre-burning, the pattern of LFVP presomas is relatively relatively regular, has part lattice to be formed；Sinter
LFVP finished products after are in granular form, average grain diameter 500-600nm；When using the LFVP finished products to coat particle diameter as 10-15 μ
During m nearly spherical nickle cobalt lithium manganate, smooth surface, regular shape, structure can be formed compared with positive electrode (such as Fig. 4 that consolidation is stablized
It is shown), particle diameter is about 15 μm.It is computed, in gained positive electrode, the mass ratio of phosphoric acid vanadium iron lithium and nickle cobalt lithium manganate is 1：
16, the thickness of clad (phosphoric acid vanadium iron lithium) is 510nm.
XRD tests are carried out to the positive electrode simultaneously, test result is as shown in Figure 5.It is from figure 5 it can be seen that of the invention
The X-ray diffraction peak intensity of anode active material of lithium ion battery made from embodiment 1 is big, sharp, lithium ion made from explanation
Cell positive material has good crystallinity, tests reference standard PDF cards, finds the anode material for lithium-ion batteries simultaneously
Characteristic spectrum with LFVP and nickle cobalt lithium manganate, illustrate the obtained anode active material of lithium ion battery of the present invention by LFVP and
Nickle cobalt lithium manganate is combined.
By lithium ion battery made from the embodiment of the present invention 1 in 4.3-2.7V voltage range, charge-discharge test is carried out,
It is about 173.6mAh/g to measure its gram volume of electric discharge first under 0.2C multiplying power；First charge-discharge efficiency is calculated, is filled first
Discharge capacity/initial charge the capacity of discharging efficiency=first.The first charge-discharge efficiency that the battery is calculated reaches 90.2%.
The gram volume of battery anode active material provided by the invention is high, and discharge platform is stable, superior performance.
By made from embodiment 1 lithium ion battery carry out cycle performance test, charge and discharge voltage is 4.3-2.7V, measure its
It is 98.5% that 1.0C, which circulates 100 capability retentions, illustrates that its cycle performance is good.Measure lithium-ion electric made from embodiment 1
Mean voltage of the pond under 1.0C is 3.74V.
Embodiment 2：
A kind of preparation method of anode active material of lithium ion battery, comprises the following steps：
(1) phosphoric acid ferrovanadium lithium presoma is prepared
Vanadic anhydride 0.092g is weighed, 5mL hydrogen peroxide stirring fully dissolving is added, obtains vanadium source solution；Weigh carbonic acid
Lithium 7.46g, ferric nitrate 81.2g, ammonium dihydrogen phosphate 23.24g, after being dissolved in 30mL nitric acid, the vanadium source solution dissolved is added, is weighed
2.11g citric acids each material will be complexed as complexing agent, after stirring 2h, obtained mixed slurry will be carried out at 150 DEG C above
Vacuum drying, obtains phosphoric acid ferrovanadium lithium (LFVP) presoma.
(2) pre-burning of LFVP presomas：By dried LFVP precursor powders under nitrogen atmosphere protection, with 5 DEG C/minute
The speed of clock is warming up to 250 DEG C, is incubated 3h, obtains the LFVP precursor powders after pre-burning.
(3) ternary raw material/phosphoric acid ferrovanadium lithium presoma mixing：LFVP precursor powders after 5.6g pre-burnings are added to
Stirring and dissolving 0.5h in 60g alcohol, obtains the dispersion liquid of LFVP presomas；
Weigh 100g nickel-cobalt-manganese ternary material Li (Ni0.5Co0.2Mn0.3)O2(average grain diameter is 12.4 μm), is added to
State after continuing to stir 1.5h in the alcohol dispersion liquid of LFVP presomas, gained slurry is dried in vacuo 1h at 100 DEG C, mixed
Close powder；
(4) prepared by ternary raw material/phosphoric acid ferrovanadium lithium composite positive pole：By dried mixed-powder in a nitrogen atmosphere
Multi-steps sintering, 150 DEG C, Isothermal sinter 2h first are warming up to 2 DEG C/min speed, then are heated up with 2 DEG C/min speed 600
DEG C, Isothermal sinter 10h, the composite positive pole of clad structure is obtained after furnace cooling.
The preparation method of lithium ion battery is the same as embodiment 1.
It is computed, in gained positive electrode, the mass ratio of phosphoric acid vanadium iron lithium and nickle cobalt lithium manganate is 1：18.5 clad
The thickness of (phosphoric acid vanadium iron lithium) is 430nm.
Embodiment 3：
A kind of preparation method of anode active material of lithium ion battery, comprises the following steps：
(1) vanadium phosphate oxygen lithium presoma is prepared
Ammonium metavanadate 4.68g is weighed, ammonium dihydrogen phosphate 4.60g, oxalic acid 20.82g, is dissolved in 350mL deionized water,
2h is stirred in 70 DEG C of water-baths, fully dissolving；Then 0.99g lithium hydroxides and 1.0g sucrose are added, continues stirring reaction 10h
Afterwards, mixed slurry is obtained；Gained mixed slurry is subjected to vacuum drying 4h at 100 DEG C, obtains vanadium phosphate oxygen lithium (LiOVPO4)
Presoma.
(2)LiOVPO4The pre-burning of presoma：By dried LiOVPO4Precursor powder is under nitrogen atmosphere protection, with 4
DEG C/min speed be warming up to 300 DEG C, be incubated 2h, obtain the LiOVPO after pre-burning4Precursor powder.
(3) vanadyl phosphate lithium finished product is prepared：LiOVPO to after above-mentioned pre-burning4In presoma, with ball powder ratio 10:1 adds
Agate bead, ball milling refinement 350rpm/2h, the LiOVPO after ball milling are carried out to precursor powder with agate grinding pot4Presoma
Particle diameter is about 700nm.
By the LiOVPO after refinement4Precursor powder is in 10% (volume fraction) O2And 90%N2Under the mixed gas of composition
Multi-steps sintering, 200 DEG C, Isothermal sinter 2h first are warming up to 2 DEG C/min speed, then are heated up with 1 DEG C/min speed 550
DEG C, Isothermal sinter 12h, after furnace cooling, obtain vanadyl phosphate lithium (LiOVPO4) finished product.
(4) prepared by ternary raw material/vanadyl phosphate lithium composite positive pole
11.3g gained vanadyl phosphate lithium is added in 100g alcohol, and adds 3g polyethylene glycol and 0.8g super
P stirring and dissolvings 1h；Obtain the dispersion liquid of coating layer material；
Weigh 100g nickel-cobalt-manganese ternary material Li (Ni0.5Co0.2Mn0.3)O2(average grain diameter is 13.9 μm), is added to
State after continuing to stir 4h in solution, 0.5h is centrifuged with 1000rpm rotating speeds to gained slurry, supernatant is removed, precipitation is collected, by institute
It must be deposited at 120 DEG C and be dried in vacuo 1h, obtain the nickel cobalt manganese of the composite positive pole of clad structure, i.e. vanadium phosphate oxygen lithium cladding
Sour lithium.
It is computed, in gained positive electrode, the mass ratio of vanadium phosphate oxygen lithium and nickle cobalt lithium manganate is 1：8.8, clad (phosphorus
Sour vanadium iron lithium) thickness be 500nm.
Embodiment 4
A kind of preparation method of anode active material of lithium ion battery, comprises the following steps：
(1) vanadium phosphate oxygen lithium presoma is prepared：
Vanadic anhydride 5.46g, ammonium dihydrogen phosphate 6.91g, oxalic acid 25.11g are weighed, is dissolved in 400mL deionized water
In, 2.5h is stirred in 65 DEG C of water-baths, fully dissolving；Then 2.33g lithium carbonates and 2g glucose are added, continues stirring reaction
After 10h, mixed slurry is obtained；Gained mixed slurry is subjected to vacuum drying 4h at 100 DEG C, obtains vanadyl phosphate lithium
(LiVOPO4) presoma.
(2)LiOVPO4The pre-burning of presoma：By dried LiOVPO4Precursor powder is under nitrogen atmosphere protection, with 4
DEG C/min speed be warming up to 300 DEG C, be incubated 2h, obtain the LiOVPO after pre-burning4Precursor powder.
(3) ternary raw material/vanadyl phosphate lithium presoma mixing：By the LiOVPO after 10.9g pre-burnings4Precursor powder adds
Into 60g alcohol, stirring and dissolving 1h, obtains LiOVPO4The dispersion liquid of presoma；
Weigh 100g nickel-cobalt-manganese ternary material Li (Ni0.5Co0.2Mn0.3)O2(average grain diameter is 14.2 μm), is added to
State LiOVPO4Continue in the alcohol dispersion liquid of presoma after stirring 1.5h, gained slurry is dried in vacuo 1h at 100 DEG C, obtained
To mixed-powder；
(4) prepared by ternary raw material/vanadyl phosphate lithium composite positive pole
By dried mixed-powder in 10%O2+ 90%N2Multi-steps sintering under the mixed atmosphere of composition, first with 2 DEG C/min
Speed be warming up to 200 DEG C, Isothermal sinter 2h, then with 1 DEG C/min speed heating at 550 DEG C, Isothermal sinter 12h is cold with stove
But the nickle cobalt lithium manganate of the composite positive pole of clad structure, i.e. vanadium phosphate oxygen lithium cladding is obtained afterwards.
It is computed, in gained positive electrode, the mass ratio of vanadium phosphate oxygen lithium and nickle cobalt lithium manganate is 1：19, clad (phosphorus
Sour vanadium oxygen lithium) thickness be 650nm.Vanadium phosphate oxygen lithium layer is discontinuous to be attached to nickle cobalt lithium manganate surface；Vanadium phosphate oxygen lithium layer
The area of cladding accounts for the 85% of the nickle cobalt lithium manganate total surface area.
For prominent beneficial effects of the present invention, following comparative example now is set for embodiment 1：
Comparative example 1
To nickel-cobalt-manganese ternary material Li (Ni0.5Co0.2Mn0.3)O2It is without any processing.
The ball milling mixing (being not added with film forming agent and solvent) of the ternary raw material of comparative example 2+phosphoric acid ferrovanadium lithium finished product：
Weigh 100g nickel-cobalt-manganese ternary material Li (Ni0.5Co0.2Mn0.3)O2(average grain diameter is 14.5 μm), 6.4g phosphorus
Sour ferrovanadium lithium finished product (average grain diameter 500-600nm), with ball powder ratio 10:1 adds agate bead, with agate grinding pot to mixed powder
End carries out ball milling mixing 300rpm/2h, and sieve 300 eye mesh screens after ball milling, obtains positive electrode.
The ternary raw material of comparative example 3+vanadyl phosphate lithium finished product is stirred：
Weigh 100g nickel-cobalt-manganese ternary material Li (Ni0.5Co0.2Mn0.3)O2(average grain diameter is 14.5 μm), 6.4g phosphorus
Sour vanadyl lithium finished product (average grain diameter 500-600nm), the deionized water for adding 150mL dissolve as solvent, the magnetic at 25 DEG C
Power stirs 300rpm/2h, and 1h is then dried in vacuo at 120 DEG C, and 300 eye mesh screens that sieve, and obtains positive electrode.
Performance will be carried out using battery made from battery made from above-described embodiment 1-4 positive electrode and comparative example 1-3
Test, it is as a result as shown in table 1 below.
Table 1
Wherein, the thermal discharge (J/g) in upper table 1 is obtained with DSC methods (differential scanning calorimetry) measuring stability.It is hot steady
Qualitative is a basic problem of lithium ion battery security, and battery security is mainly relevant with the thermal activities of electrode material, one
As situation when thinking battery temperature rise, many exothermic reactions can occur for inside, when caused heat has exceeded heat in itself
Scatter and disappear, battery will occur " thermal runaway ".DSC (is to measure the relation between the temperature of material internal heat deflection and hot-fluid.
Above example 1-3 and comparative example 1-3 electrode slice are assembled into CR2025 type button cells respectively, at room temperature
4.3V is charged to 1C multiplying powers, battery is removed, takes battery apart in Ar gas glove boxes, by the active matter on plus plate current-collecting body
Matter is peeled off, and after weighing quality, is put into aluminium crucible and is sealed, then take out and be put into DSC instruments, carry out DSC under nitrogen protection
Test, for temperature range at 30~500 DEG C, 5 DEG C/min of heating rate, test result is as shown in Figure 6.Calculated according to Fig. 6 curve
Go out the thermal discharge (J/g) of each sample.
From table 1 it follows that compared to conventional comparative's example, covering property positive electrode prepared by the present invention has good
Mean voltage when processing characteristics, higher specific capacity is showed in discharge process, and discharged is high, brings higher energy density.
Close positive electrode, well-formed are coated, top layer avoids direct contact with electrolyte, reduces erosion, increases cyclical stability.
Heat endurance after cladding also has clear improvement.
Embodiment described above only expresses the several embodiments of the present invention, and its description is more specific and detailed, but simultaneously
Therefore the limitation to the scope of the claims of the present invention can not be interpreted as.It should be pointed out that for one of ordinary skill in the art
For, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to the guarantor of the present invention
Protect scope.Therefore, the protection domain of patent of the present invention should be determined by the appended claims.
Claims (10)
1. a kind of anode material for lithium-ion batteries, it is characterised in that the anode material for lithium-ion batteries includes nickle cobalt lithium manganate
With the clad for being arranged on the nickle cobalt lithium manganate surface, wherein, the material of the clad is phosphoric acid ferrovanadium lithium or phosphoric acid oxygen
Vanadium lithium.
2. anode material for lithium-ion batteries as claimed in claim 1, it is characterised in that the material of the clad and the nickel
The mass ratio of cobalt manganic acid lithium is 1：(5.7-19).
3. anode material for lithium-ion batteries as claimed in claim 1, it is characterised in that the thickness of the clad is 200-
700nm。
4. anode material for lithium-ion batteries as claimed in claim 1, it is characterised in that the clad is discontinuous to be attached to
Nickle cobalt lithium manganate surface.
5. a kind of preparation method of anode material for lithium-ion batteries, it is characterised in that comprise the following steps：
Coating layer material is provided, the coating layer material is phosphoric acid ferrovanadium lithium or vanadyl phosphate lithium；
The first solvent and film forming agent are added into the coating layer material, after being well mixed, obtains the dispersion liquid of coating layer material,
Add nickle cobalt lithium manganate and carry out mixing 0.5-4h, it is solid to drying gained by gained mixture after 90-160 DEG C of vacuum drying
Body thing is sieved with 300-400 mesh, obtains anode material for lithium-ion batteries, the anode material for lithium-ion batteries includes nickel cobalt mangaic acid
Lithium and the clad for being arranged on the nickle cobalt lithium manganate surface；The film forming agent include polyvinyl alcohol, polyethylene glycol, PVP,
At least one of neopelex and stearic acid.
6. the preparation method of anode material for lithium-ion batteries as claimed in claim 5, it is characterised in that the coating layer material
Preparation process it is as follows：There is provided coating layer material presoma, under protective gas, by the coating layer material presoma in
200-400 DEG C of constant temperature pre-burning 2-4h, the coating layer material presoma after pre-burning is then subjected to ball milling, then by the cladding after ball milling
Layer material presoma is sintered；Wherein, the detailed process of the sintering is：150-250 DEG C is first warming up to, an Isothermal sinter
1-2h, then heat up at 550-700 DEG C, secondary Isothermal sinter 6-12h.
7. the preparation method of anode material for lithium-ion batteries as claimed in claim 6, it is characterised in that when the clad material
Expect for phosphoric acid ferrovanadium lithium when, the preparation process of the coating layer material presoma is as follows：By lithium source, vanadium source, source of iron, phosphorus source massage
You compare Li：Fe：V：P=1：a：b：1 is weighed, and is added the second solvent, complexing agent, is obtained mixed slurry after mixing is scattered, adjust
The pH for saving the mixed slurry is 1-7, and gained mixed slurry is dried in vacuo at 90-160 DEG C, obtains phosphoric acid ferrovanadium lithium
Presoma；Wherein, the ＜ b ＜ 2/3 of 0 ＜ a ＜ 1,0, and 2a+3b=2.
8. the preparation method of anode material for lithium-ion batteries as claimed in claim 6, it is characterised in that when the clad material
Expect for vanadyl phosphate lithium when, the preparation process of the coating layer material presoma is as follows：By lithium source, vanadium source, phosphorus source, second molten
Agent, mixed with complexing agent and/or reducing agent, the stirring in water bath at 65-100 DEG C, obtain mixed slurry, by gained mixed slurry
It is dried in vacuo at 90-160 DEG C, obtains vanadyl phosphate lithium presoma.
9. a kind of preparation method of anode material for lithium-ion batteries, it is characterised in that comprise the following steps：
Coating layer material presoma is provided, before the coating layer material presoma is phosphoric acid ferrovanadium lithium presoma or vanadyl phosphate lithium
Drive body；Under protective gas, by the coating layer material presoma at 200-400 DEG C constant temperature pre-burning 2-4h, after cooling, obtain
Coating layer material presoma after to pre-burning；
Coating layer material presoma after the pre-burning is dissolved in water soluble polar solvent, nickle cobalt lithium manganate is added thereto and enters
Row mixing 0.5-10h, obtains the first slurry, by first slurry in 90-160 DEG C of vacuum drying, obtains positive electrode forerunner
Body；
The positive electrode material precursor is sintered, the detailed process of the sintering is：150-250 DEG C is first warming up to, once
Isothermal sinter 1-2h, then heat up at 550-700 DEG C, secondary Isothermal sinter 6-12h；After cooling, to sintering gained solids with
300-400 mesh sieves, and obtains anode material for lithium-ion batteries, and the anode material for lithium-ion batteries includes nickle cobalt lithium manganate and set
Put the clad on the nickle cobalt lithium manganate surface.
10. a kind of lithium ion battery, it is characterised in that the lithium ion battery is included as any one of claim 1-4
Anode material for lithium-ion batteries.
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108878859A (en) * | 2018-06-07 | 2018-11-23 | 中航锂电（洛阳）有限公司 | A kind of nickel-cobalt lithium manganate cathode material and preparation method thereof, lithium ion battery |
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| TWI728447B (en) * | 2019-08-29 | 2021-05-21 | 國立清華大學 | LiFePO4 PRECURSOR FOR MANUFACTURING ELECTRODE MATERIAL OF Li-ION BATTERY AND METHOD FOR MANUFACTURING THE SAME |
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103178251A (en) * | 2013-03-15 | 2013-06-26 | 宁德新能源科技有限公司 | Anode material of lithium ion power battery and lithium ion powder battery comprising same |
| CN104577093A (en) * | 2015-01-13 | 2015-04-29 | 海宁美达瑞新材料科技有限公司 | Surface coating modified lithium ion battery cathode material and preparation method thereof |
| CN105185987A (en) * | 2014-05-29 | 2015-12-23 | 宁德新能源科技有限公司 | Positive electrode material and lithium ion secondary battery |
| CN105845909A (en) * | 2016-04-27 | 2016-08-10 | 深圳市德方纳米科技股份有限公司 | Positive electrode active material for lithium ion battery, preparation method for positive electrode active material, and lithium ion battery |
| CN105914356A (en) * | 2016-06-17 | 2016-08-31 | 中南大学 | Modification method of positive ternary material for lithium-ion battery |
| CN106784809A (en) * | 2016-11-18 | 2017-05-31 | 山东精工电子科技有限公司 | A kind of LiVOPO4/LiMPO4/ C composite material of core-shell structure and preparation method |
| CN106784726A (en) * | 2017-01-18 | 2017-05-31 | 长安大学 | Vanadyl phosphate lithium is modified lithium-rich manganese-based layered lithium ion battery positive electrode and preparation method thereof |
-
2017
- 2017-08-07 CN CN201710667570.XA patent/CN107665983B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103178251A (en) * | 2013-03-15 | 2013-06-26 | 宁德新能源科技有限公司 | Anode material of lithium ion power battery and lithium ion powder battery comprising same |
| CN105185987A (en) * | 2014-05-29 | 2015-12-23 | 宁德新能源科技有限公司 | Positive electrode material and lithium ion secondary battery |
| CN104577093A (en) * | 2015-01-13 | 2015-04-29 | 海宁美达瑞新材料科技有限公司 | Surface coating modified lithium ion battery cathode material and preparation method thereof |
| CN105845909A (en) * | 2016-04-27 | 2016-08-10 | 深圳市德方纳米科技股份有限公司 | Positive electrode active material for lithium ion battery, preparation method for positive electrode active material, and lithium ion battery |
| CN105914356A (en) * | 2016-06-17 | 2016-08-31 | 中南大学 | Modification method of positive ternary material for lithium-ion battery |
| CN106784809A (en) * | 2016-11-18 | 2017-05-31 | 山东精工电子科技有限公司 | A kind of LiVOPO4/LiMPO4/ C composite material of core-shell structure and preparation method |
| CN106784726A (en) * | 2017-01-18 | 2017-05-31 | 长安大学 | Vanadyl phosphate lithium is modified lithium-rich manganese-based layered lithium ion battery positive electrode and preparation method thereof |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11476462B2 (en) | 2011-06-22 | 2022-10-18 | National Tsing Hua University | LiFePO4 precursor for manufacturing electrode material of Li-ion battery and method for manufacturing the same |
| CN108878859A (en) * | 2018-06-07 | 2018-11-23 | 中航锂电（洛阳）有限公司 | A kind of nickel-cobalt lithium manganate cathode material and preparation method thereof, lithium ion battery |
| TWI728447B (en) * | 2019-08-29 | 2021-05-21 | 國立清華大學 | LiFePO4 PRECURSOR FOR MANUFACTURING ELECTRODE MATERIAL OF Li-ION BATTERY AND METHOD FOR MANUFACTURING THE SAME |
| CN110828803A (en) * | 2019-12-24 | 2020-02-21 | 贵州梅岭电源有限公司 | Method for preparing LCO/NCA composite positive electrode material |
| CN111554907A (en) * | 2020-05-15 | 2020-08-18 | 深圳澳睿新能源科技有限公司 | Application of fatty acid in preparation of lithium ion battery and method for preparing electrode material |
| CN114388776A (en) * | 2021-12-06 | 2022-04-22 | 宜宾光原锂电材料有限公司 | Method for removing impurity sodium by washing nickel-cobalt-manganese ternary precursor |
| CN114180648A (en) * | 2021-12-08 | 2022-03-15 | 钱冠男 | Preparation method of lithium ion battery anode material |
| CN114447322A (en) * | 2022-01-25 | 2022-05-06 | 欣旺达电动汽车电池有限公司 | Lithium manganese iron phosphate modified cathode material and preparation method thereof |
| CN114447322B (en) * | 2022-01-25 | 2024-04-30 | 欣旺达动力科技股份有限公司 | Lithium iron manganese phosphate modified positive electrode material and preparation method thereof |
| CN115863613A (en) * | 2023-02-28 | 2023-03-28 | 四川轻化工大学 | Lithium manganese iron phosphate coated modified high-nickel positive electrode material, and preparation method and application thereof |
| CN117038996A (en) * | 2023-10-10 | 2023-11-10 | 浙江帕瓦新能源股份有限公司 | α-NaVOPO 4 Coated sodium ion battery positive electrode material, preparation method thereof and sodium ion battery |
| CN117038996B (en) * | 2023-10-10 | 2024-01-23 | 浙江帕瓦新能源股份有限公司 | α-NaVOPO 4 Coated sodium ion battery positive electrode material, preparation method thereof and sodium ion battery |
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