CN110176590A - The rich lithium presoma of spherical shape that be made of class square and its made of lithium-rich anode material and product preparation method - Google Patents
The rich lithium presoma of spherical shape that be made of class square and its made of lithium-rich anode material and product preparation method Download PDFInfo
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Abstract
The invention discloses the rich lithium presoma of spherical shape being made of class square and its made of lithium-rich anode material and product preparation method, implementation steps are as follows: 1) the special spherical rich lithium presoma that solvent-thermal method heating reaction preparation is made of class square；2) the rich lithium presoma after pre-burning is mixed with lithium carbonate, and high temperature sintering reaction prepares spherical lithium-rich anode material.PVP is added in solvent, is template in order to forming special appearance；By using urea as precipitating reagent, reacting solution pH value not only can be slowly adjusted, but also can hydrolyze to obtain carbanion, is reacted with metal ion, the special spherical rich lithium presoma being made of class square is prepared, improves the structural stability of material.The present invention is efficient, simple, and gained spherical shape lithium-rich anode material, has good structural stability and chemical property.
Description
Technical field
The present invention relates to anode material for lithium-ion batteries manufacturing technology fields, and in particular to what a type was made of square
Lithium-rich anode material made of spherical richness lithium presoma and preparation method thereof, the rich lithium presoma of spherical shape being made of square and its
Preparation method.
Background technique
Today's society, environmental pollution and energy shortage problem are increasingly severe, to promote the development of clean energy resource.Lithium
Ion battery is widely used since it has the advantages that high-energy density, high voltage and long circulation life, and is used for quotient
The auto industry of industry then needs to further increase energy density and its safety, and meeting the key factor of this challenge is to find
New high-capacity electrode material, especially positive electrode.Core material of the anode material for lithium-ion batteries as lithium ion battery
One of, there is vital effect for improving battery overall performance.In recent years, lithium-rich manganese-based tertiary cathode material:
xLi2MnO3·(1-x)LiMO2(0 < x < 1, M=Ni, Co, Mn), because it is with height ratio capacity (250 ~ 300mAh/g), high charge and discharge
The features such as level platform (> 4.5V) and become research hotspot, and manganese element content is higher in lithium-rich manganese-based anode material, reduces material
The price of material；Lithium-rich manganese-based anode material has high energy density simultaneously, be meet the power electric vehicle market demand it is ideal just
Pole material.
Synthesis process, presoma pattern and the size Control of lithium-rich manganese-based anode material, to the electricity of lithium-rich anode material
Chemical property has more significant influence.
Summary of the invention
In order to advanced optimize properties of product, the present invention provides a kind of rich lithium forerunner's system of the spherical shape being made of class square
At lithium-rich anode material, preparation method be mainly use high temperature auxiliary law combination solvent structure go out class square form
Special spherical rich lithium presoma, obtains spherical lithium-rich anode material after pre-burning and the sintering of mixed lithium, effectively improves the knot of material
Structure stability improves the cyclical stability of lithium ion battery.
The invention is realized by the following technical scheme:
A kind of rich lithium precursor preparation method of spherical shape being made of class square, comprising the following steps:
1) it prepares mixed solvent: 1.8 ~ 2.0g polyvinylpyrrolidone PVP is added according to every 80ml deionized water, at 40 ~ 60 DEG C
Lower water-bath 20 ~ 40min of heating stirring, dissolves polyvinylpyrrolidone sufficiently, forms the mixed solvent of clear viscous；
2) synthesize the rich lithium presoma of the spherical shape being made of square: molar ratio is according to the stoichiometric ratio meter for synthesizing rich lithium presoma
It calculates, weighs nickel cobalt manganese metal salt, be that 1:3.0 ~ 3.4 weigh urea by metal ion integral molar quantity and the ratio of urea mole,
The two is added to the in the mixed solvent that step 1 configures, every 80ml mixed solution corresponds to total metal ion of 8-12mmol, room temperature
30 ~ 60min of lower stirring, so that both sufficiently dissolutions, obtain transparent mixed solution, it is anti-that mixed solution is then poured into high temperature
Answer in kettle, the heating reaction 18 ~ for 24 hours at 120 ~ 160 DEG C is cooled to room temperature, filter and using deionized water and dehydrated alcohol into
Row repeatedly rinses, and product is put into vacuum oven, under vacuum 60 ~ 80 DEG C of dry 8 ~ 12h, obtains being made of square
Special spherical rich lithium carbonate precursor；By product at 450 ~ 550 DEG C 3 ~ 5h of pre-burning, obtain the special balls being made of square
Shape richness oxidate for lithium presoma.
Further preferably, Mw=1300000 of PVP.
Further preferably, the nickel cobalt manganese metal salt used in step 2 is sulfate or nitrate or hydrochloride.
The spherical shape rich lithium presoma provided by the invention being made of class square, the special balls being made of many class squares
Shape structure, the size of spherical structure are 6 ~ 9 μm.
The present invention also provides a kind of preparation method of lithium-rich anode material, the rich lithium of spherical shape being made of class square is weighed
Oxide precursor and lithium carbonate ball milling mixing are uniform, and drum's speed of rotation is 250 ~ 300 rad/min；Then heat treatment burning is carried out
Knot, program is: being warming up to 800 ~ 900 DEG C at room temperature with 3 ~ 5 DEG C/min, cools to room temperature with the furnace after keeping the temperature 10 ~ 15 h, obtain richness
Lithium anode material.
The present invention is further preferred, lithium carbonate excessive 5%.
The present invention also provides lithium-rich anode materials made from the above method.
Compared with prior art, the present invention having following obvious advantage:
One, the special spherical rich lithium presoma that the present invention is made of the synthesis of high temperature secondary solvent thermal method class square, solvent
Middle addition polyvinylpyrrolidone (PVP), functions as template, in order to form special appearance, using urea conduct
Precipitating reagent is hydrolyzed to carbanion first during the reaction, can react with metal ion and generate carbonate precursor, together
When play the role of slowly adjusting pH value, contribute to form the presoma with special construction.
Two, synthesis step of the present invention is simple, efficient, and the special spherical structure being made of many class cube structures, shape
At the structural stability of height, capacitance loss caused by reducing because of structure collapses, what the influence to performance be can not ignore, effectively change
The cyclical stability of kind lithium ion battery, has excellent chemical property.
Detailed description of the invention
Fig. 1 is the scanning electron microscope diagram for the special spherical rich lithium presoma being made of in embodiment 3 class square
(SEM).
Fig. 2 is the scanning electron microscope diagram (SEM) of the rich lithium presoma of ordinary precipitation process preparation in comparative example 2.
Fig. 3 is the scanning electron microscope diagram for the special spherical lithium-rich anode material being made of in embodiment 3 class square
(SEM).
Specific embodiment
Lithium-rich anode material made from a kind of special spherical rich lithium presoma being made of class square, preparation method tool
Body follows the steps below to implement:
1) preparation of mixed solvent: 1.8 ~ 2.0g polyvinylpyrrolidone (PVP) (Mw=1300000) is weighed in the beaker of 100ml
In, the deionized water of 80ml is added into beaker, 20 ~ 40min of water-bath heating stirring, makes polyvinylpyrrolidine at 40 ~ 60 DEG C
Ketone sufficiently dissolves, and forms the mixed solvent of clear viscous；
2) synthesis for the special spherical rich lithium presoma being made of square: weighing suitable nickel cobalt manganese metal salt, (molar ratio is pressed
Calculated according to the stoichiometric ratio for synthesizing rich lithium presoma), then weighing suitable urea, (metal ion integral molar quantity rubs with urea
You amount ratio be 1:(3.0 ~ 3.4)), the two is added to the in the mixed solvent configured in step 1), at room temperature stir 30 ~
60min, so that both sufficiently dissolutions, obtain transparent mixed solution, mixed solution is then poured into Teflon polytetrafluoroethyl-ne
In alkene pyroreaction kettle, the heating reaction 18 ~ for 24 hours at 120 ~ 160 DEG C is cooled to room temperature, filters and simultaneously use deionized water and nothing
Water-ethanol is repeatedly rinsed, and product is put into vacuum oven, and 60 ~ 80 DEG C of dry 8 ~ 12h, obtain by pros under vacuum
The special spherical rich lithium carbonate precursor of body composition；By product at 450 ~ 550 DEG C 3 ~ 5h of pre-burning, obtain being made of square
Special spherical rich oxidate for lithium presoma；
3) preparation of lithium-rich anode material: uniform (its of oxide precursor and lithium carbonate ball milling mixing after weighing appropriate pre-burning
Middle lithium carbonate is excessive 5%), and drum's speed of rotation is 250 ~ 300 rad/min, and the sintering procedure of heat treatment is: at room temperature with 3 ~ 5 DEG C/
Min is warming up to 800 ~ 900 DEG C, cools to room temperature with the furnace after keeping the temperature 10 ~ 15 h, obtains lithium-rich anode material.
Embodiment 1
The special spherical rich lithium presoma and its lithium-rich anode material 0.3Li being made of class square2MnO3·
0.7LiNi0.5Co0.2Mn0.3O2Preparation
1, the preparation of mixed solvent: weighing 1.8g polyvinylpyrrolidone (PVP) (Mw=1300000) in the beaker of 100ml,
Suitable deionized water is added into beaker, the water-bath heating stirring 20min at 40 DEG C keeps polyvinylpyrrolidone sufficiently molten
Solution, forms the mixed solvent of clear viscous.
2, the synthesis for the special spherical rich lithium presoma being made of square: according to 0.3Li2MnO3·
0.7LiNi0.5Co0.2Mn0.3O2Rich lithium material each element ratio weighs suitable nickel cobalt manganese metal salt, and (molar ratio is rich according to synthesis
The stoichiometric ratio of lithium presoma calculates), then weigh suitable urea (ratio of metal ion integral molar quantity and urea mole
Value is 1:3.0), the two is added to the in the mixed solvent configured in step 1), stirs 30min at room temperature, so that both filling
Divide dissolution, obtains transparent mixed solution, then pour into mixed solution in Teflon polytetrafluoroethylene (PTFE) pyroreaction kettle,
Heating reaction 18h, is cooled to room temperature at 120 DEG C, filters and is repeatedly rinsed using deionized water and dehydrated alcohol, by product
It is put into vacuum oven, under vacuum 60 DEG C of dry 8h, obtains the special spherical rich lithium carbonic acid salt precursor being made of square
Body；By product at 450 DEG C pre-burning 3h, the special spherical rich oxidate for lithium presoma for obtaining being made of square.
3, the preparation of lithium-rich anode material: the oxide precursor and lithium carbonate ball milling mixing after weighing appropriate pre-burning are uniform
(wherein lithium carbonate excessive 5%), drum's speed of rotation is 250 rad/min, and the sintering procedure of heat treatment is: at room temperature with 3 DEG C/min
800 DEG C are warming up to, room temperature is cooled to the furnace after keeping the temperature 10 h, obtains lithium-rich anode material.
Embodiment 2
The special spherical rich lithium presoma and its lithium-rich anode material 0.4Li being made of class square2MnO3·
0.6LiNi0.5Co0.2Mn0.3O2Preparation
1, the preparation of mixed solvent: weighing 2.0g polyvinylpyrrolidone (PVP) (Mw=1300000) in the beaker of 100ml,
Suitable deionized water is added into beaker, the water-bath heating stirring 30min at 50 DEG C keeps polyvinylpyrrolidone sufficiently molten
Solution, forms the mixed solvent of clear viscous.
2, the synthesis for the special spherical rich lithium presoma being made of square: according to 0.4Li2MnO3·
0.6LiNi0.5Co0.2Mn0.3O2Rich lithium material each element ratio weighs suitable nickel cobalt manganese metal salt, and (molar ratio is rich according to synthesis
The stoichiometric ratio of lithium presoma calculates), then weigh suitable urea (ratio of metal ion integral molar quantity and urea mole
Value is 1:3.2), the two is added to the in the mixed solvent configured in step 1), stirs 45min at room temperature, so that both filling
Divide dissolution, obtains transparent mixed solution, then pour into mixed solution in Teflon polytetrafluoroethylene (PTFE) pyroreaction kettle,
Heating reaction 20h, is cooled to room temperature at 140 DEG C, filters and is repeatedly rinsed using deionized water and dehydrated alcohol, by product
It is put into vacuum oven, under vacuum 70 DEG C of dry 10h, obtains the special spherical rich lithium carbonic acid salt precursor being made of square
Body；By product at 500 DEG C pre-burning 4h, the special spherical rich oxidate for lithium presoma for obtaining being made of square.
3, the preparation of lithium-rich anode material: the oxide precursor and lithium carbonate ball milling mixing after weighing appropriate pre-burning are uniform
(wherein lithium carbonate excessive 5%), drum's speed of rotation is 250 rad/min, and the sintering procedure of heat treatment is: at room temperature with 3 DEG C/min
850 DEG C are warming up to, room temperature is cooled to the furnace after keeping the temperature 12h, obtains lithium-rich anode material.
Embodiment 3
The special spherical rich lithium presoma and its lithium-rich anode material 0.5Li being made of class square2MnO3·
0.5LiNi0.5Co0.2Mn0.3O2Preparation
1, the preparation of mixed solvent: weighing 2.0g polyvinylpyrrolidone (PVP) (Mw=1300000) in the beaker of 100ml,
Suitable deionized water is added into beaker, the water-bath heating stirring 40min at 60 DEG C keeps polyvinylpyrrolidone sufficiently molten
Solution, forms the mixed solvent of clear viscous.
2, the synthesis for the special spherical rich lithium presoma being made of square: according to 0.5Li2MnO3·
0.5LiNi0.5Co0.2Mn0.3O2Rich lithium material each element ratio weighs suitable nickel cobalt manganese metal salt, and (molar ratio is rich according to synthesis
The stoichiometric ratio of lithium presoma calculates), then weigh suitable urea (ratio of metal ion integral molar quantity and urea mole
Value is 1:3.4), the two is added to the in the mixed solvent configured in step 1), stirs 60min at room temperature, so that both filling
Divide dissolution, obtains transparent mixed solution, then pour into mixed solution in Teflon polytetrafluoroethylene (PTFE) pyroreaction kettle,
Heating reaction for 24 hours, is cooled to room temperature at 160 DEG C, filters and is repeatedly rinsed using deionized water and dehydrated alcohol, by product
It is put into vacuum oven, under vacuum 80 DEG C of dry 12h, obtains the special spherical rich lithium carbonic acid salt precursor being made of square
Body；By product at 550 DEG C pre-burning 5h, the special spherical rich oxidate for lithium presoma for obtaining being made of square.
3, the preparation of lithium-rich anode material: the oxide precursor and lithium carbonate ball milling mixing after weighing appropriate pre-burning are uniform
(wherein lithium carbonate excessive 5%), drum's speed of rotation is 300 rad/min, and the sintering procedure of heat treatment is: at room temperature with 5 DEG C/min
900 DEG C are warming up to, room temperature is cooled to the furnace after keeping the temperature 15 h, obtains lithium-rich anode material.
Comparative example 1
Lithium-rich anode material 0.3Li2MnO3·0.7LiNi0.5Co0.2Mn0.3O2Preparation
1, precursor preparation: NiSO4·6H2O, CoSO4·7H2O, MnSO4·H2O is according to 0.3Li2MnO3·
0.7LiNi0.5Co0.2Mn0.3O2Rich lithium material each element ratio weighs, and dissolution in deionized water, is configured to concentration of metal ions
For the solution of 1.0mol/L, certain density sodium carbonate liquor is added drop-wise in metal ion solution, pH value is adjusted to 7.5, stirs
It mixes precipitating 20 hours, filter and is repeatedly rinsed using deionized water and dehydrated alcohol, and dried at 80 DEG C, obtain carbonic acid
Salt precursor body, 550 DEG C carry out calcining 5h, and heating rate is 3 DEG C/min, and sieving obtains spherical oxidation of precursor object；
2, prepared by lithium-rich anode material: the oxide precursor and lithium carbonate ball milling mixing after weighing appropriate pre-burning are uniform (wherein
Lithium carbonate is excessive 5%), milling parameters are as follows: revolving speed is 250 r/min, and the time is 2 h.Presoma and lithium carbonate are uniformly mixed
Afterwards, it being sintered, heating rate is 3 DEG C/min, 900 DEG C of heat preservation 12 h, 900-500 DEG C of rate of temperature fall control is 3 DEG C/
Then min cools to room temperature with the furnace, lithium-rich anode material is prepared.
Comparative example 2
Lithium-rich anode material 0.4Li2MnO3·0.6LiNi0.5Co0.2Mn0.3O2Preparation
1, precursor preparation: NiSO4·6H2O, CoSO4·7H2O, MnSO4·H2O is according to 0.4Li2MnO3·
0.6LiNi0.5Co0.2Mn0.3O2Rich lithium material each element ratio weighs, and dissolution in deionized water, is configured to concentration of metal ions
For the solution of 1.0mol/L, certain density sodium carbonate liquor is added drop-wise in metal ion solution, pH value is adjusted to 7.5, stirs
It mixes precipitating 22 hours, filter and is repeatedly rinsed using deionized water and dehydrated alcohol, and dried at 80 DEG C, obtain carbonic acid
Salt precursor body, 550 DEG C carry out calcining 5h, and heating rate is 3 DEG C/min, and sieving obtains spherical oxidation of precursor object；
2, prepared by lithium-rich anode material: the oxide precursor and lithium carbonate ball milling mixing after weighing appropriate pre-burning are uniform (wherein
Lithium carbonate is excessive 5%), milling parameters are as follows: revolving speed is 250 r/min, and the time is 2 h.Presoma and lithium carbonate are uniformly mixed
Afterwards, it being sintered, heating rate is 3 DEG C/min, 900 DEG C of heat preservation 12 h, 900-500 DEG C of rate of temperature fall control is 3 DEG C/
Then min cools to room temperature with the furnace, lithium-rich anode material is prepared.
Comparative example 3
Lithium-rich anode material 0.5Li2MnO3·0.5LiNi0.5Co0.2Mn0.3O2Preparation
1, precursor preparation: NiSO4·6H2O, CoSO4·7H2O, MnSO4·H2O is according to 0.5Li2MnO3·
0.6LiNi0.5Co0.2Mn0.3O2Rich lithium material each element ratio weighs, and dissolution in deionized water, is configured to concentration of metal ions
For the solution of 1.0mol/L, certain density sodium carbonate liquor is added drop-wise in metal ion solution, pH value is adjusted to 7.5, stirs
It mixes precipitating 24 hours, filter and is repeatedly rinsed using deionized water and dehydrated alcohol, and dried at 80 DEG C, obtain carbonic acid
Salt precursor body, 550 DEG C carry out calcining 5h, and heating rate is 3 DEG C/min, and sieving obtains spherical oxidation of precursor object；
2, prepared by lithium-rich anode material: the oxide precursor and lithium carbonate ball milling mixing after weighing appropriate pre-burning are uniform (wherein
Lithium carbonate is excessive 5%), milling parameters are as follows: revolving speed is 250 r/min, and the time is 2 h.Presoma and lithium carbonate are uniformly mixed
Afterwards, it being sintered, heating rate is 3 DEG C/min, 900 DEG C of heat preservation 12 h, 900-500 DEG C of rate of temperature fall control is 3 DEG C/
Then min cools to room temperature with the furnace, lithium-rich anode material is prepared.
Morphology characterization:
Fig. 1 is the scanning electron microscope diagram (SEM) of rich lithium presoma in embodiment 3, and Fig. 2 is ordinary precipitation process in comparative example 2
The scanning electron microscope diagram (SEM) of the rich lithium presoma of preparation, Fig. 3 are the scanning electrons of lithium-rich anode material in embodiment 3
Microscope figure (SEM).As shown in Figure 1, the special spherical structure that the rich lithium presoma of embodiment 3 is made of many class squares,
The size of spherical structure is about 6 ~ 9 μm；As shown in Fig. 2, the rich lithium presoma of 2 ordinary precipitation process of comparative example preparation is that diameter is about
3 ~ 4 μm of spherical structures, surface with rounded structures are smooth；As shown in figure 3, major part is still after 3 presoma of embodiment mixes lithium high temperature sintering
The spherical morphology of square composition is kept, though size has a little reduction, part square pattern weakens, and forms many sizes not
Deng primary granule, surface is more coarse.
Electrochemical property test:
It is sunk with the lithium-rich anode material for the special spherical rich lithium precursor preparation being made of in examples detailed above class square with common
The lithium-rich anode material of shallow lake method preparation is as ternary cathode material of lithium ion battery.By active material, conductive black Super-P
Carbon and binder PVDF is mixed according to the mass ratio of 90:5:5, is adjusted according to viscosity and N-Methyl pyrrolidone is added
(NMP) amount after 120 DEG C of vacuum drying, is sliced, compacting obtains anode under 10Mpa after mixing coated on aluminium foil
Piece.Negative electrode tab, polypropylene diaphragm, gasket and electrolyte prepared by obtained positive plate, metal lithium sheet are being full of high-purity argon
It is assembled in the glove box of gas, obtains CR2032 type button experimental cell, constant current charge-discharge is carried out on battery test system
It can test.
What table 1 provided is the rich lithium that the method for the present invention prepares several lithium-rich anode material embodiments and ordinary precipitation process preparation
The experimental data comparison that positive electrode comparative example measures, as can be seen from Table 1:
Richness prepared by the lithium-rich anode material and ordinary precipitation process for the special spherical rich lithium precursor preparation being made of class square
Lithium anode material is as anode material for lithium-ion batteries, when carrying out electro-chemical test, the first discharge specific capacity of battery and common
The lithium-rich anode material of precipitation method preparation is compared, and gap is little；But when carrying out loop test, when being recycled under 1.0C multiplying power,
After 100 circle circulations, the capacity retention ratio gap of embodiment and comparative example material is smaller, the special balls being made of class square
The lithium-rich anode material of shape richness lithium precursor preparation is slightly above the lithium-rich anode material of ordinary precipitation process preparation；With circulating ring number
Increasing, the lithium-rich anode material for the special spherical rich lithium precursor preparation being made of class square gradually shows advantage, due to
Its structure is more stable, after 200 circle circulations, by the lithium-rich anode for the special spherical rich lithium precursor preparation that class square forms
Material still keeps high capacity retention ratio.
Table 1
Claims (7)
1. a kind of rich lithium precursor preparation method of spherical shape being made of class square, which comprises the following steps:
1) it prepares mixed solvent: 1.8 ~ 2.0g polyvinylpyrrolidone PVP is added according to every 80ml deionized water, at 40 ~ 60 DEG C
Lower water-bath 20 ~ 40min of heating stirring, dissolves polyvinylpyrrolidone sufficiently, forms the mixed solvent of clear viscous；
2) synthesize the rich lithium presoma of the spherical shape being made of square: molar ratio is according to the stoichiometric ratio meter for synthesizing rich lithium presoma
It calculates, weighs nickel cobalt manganese metal salt, be that 1:3.0 ~ 3.4 weigh urea by metal ion integral molar quantity and the ratio of urea mole,
The two is added to the in the mixed solvent that step 1 configures, every 80ml mixed solution corresponds to total metal ion of 8-12mmol, room temperature
30 ~ 60min of lower stirring, so that both sufficiently dissolutions, obtain transparent mixed solution, it is anti-that mixed solution is then poured into high temperature
Answer in kettle, the heating reaction 18 ~ for 24 hours at 120 ~ 160 DEG C is cooled to room temperature, filter and using deionized water and dehydrated alcohol into
Row repeatedly rinses, and product is put into vacuum oven, under vacuum 60 ~ 80 DEG C of dry 8 ~ 12h, obtains being made of square
Special spherical rich lithium carbonate precursor；By product at 450 ~ 550 DEG C 3 ~ 5h of pre-burning, obtain the special balls being made of square
Shape richness oxidate for lithium presoma.
2. a kind of rich lithium precursor preparation method of spherical shape being made of class square according to claim 1, feature exist
In: Mw=1300000 of PVP.
3. a kind of rich lithium precursor preparation method of spherical shape being made of class square according to claim 1, feature exist
In: the nickel cobalt manganese metal salt used in step 2 is sulfate or nitrate or hydrochloride.
4. preparing the resulting rich lithium presoma of the spherical shape being made of class square by claim 1 method, it is characterised in that: by being permitted
The special spherical structure of multiclass square composition, the size of spherical structure are 6 ~ 9 μm.
5. the preparation method of lithium-rich anode material, it is characterised in that: weigh the rich lithium of spherical shape that claim 4 is made of class square
Oxide precursor and lithium carbonate ball milling mixing are uniform, and drum's speed of rotation is 250 ~ 300 rad/min；Then heat treatment burning is carried out
Knot, program is: being warming up to 800 ~ 900 DEG C at room temperature with 3 ~ 5 DEG C/min, cools to room temperature with the furnace after keeping the temperature 10 ~ 15 h, obtain richness
Lithium anode material.
6. the preparation method of lithium-rich anode material according to claim 5, it is characterised in that: lithium carbonate excessive 5%.
7. preparing resulting lithium-rich anode material according to claim 5 or 6 methods.
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| CN201910466718.2A CN110176590B (en) | 2019-05-31 | 2019-05-31 | Spherical lithium-rich precursor composed of similar cubes, lithium-rich cathode material prepared from spherical lithium-rich precursor and preparation method of product |
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