CN107248576A - A kind of low nickelic ball-shaped lithium-ion battery anode material of cation mixing and preparation method thereof - Google Patents
A kind of low nickelic ball-shaped lithium-ion battery anode material of cation mixing and preparation method thereof Download PDFInfo
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- 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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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
- H01M4/0471—Processes of manufacture in general involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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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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Abstract
The invention discloses a kind of low nickelic ball-shaped lithium-ion battery anode material of cation mixing and preparation method thereof, it is characterised in that including being Ni by chemical formulaxCoyMn1‑x‑y(OH)2Nickelic presoma mixed with Li source compound, preheat, heated up after preheating, insulation cools after insulation, annealing, the step of cooling；Wherein, wherein, 0.5<x<1, x+y<1.The present invention makes persursor material and lithium salts merge complete by the pre-heat treatment；By oxygen-enriched air roasting, oxidation process makes the nickel ion complete oxidation of low price, it is to avoid dephasign is generated；By process annealing, improve the sequence of crystal cationic, make crystal structure more orderly, lift the chemical property of material.
Description
Technical field
The present invention relates to anode material for lithium-ion batteries, more specifically a kind of nickelic ball-shaped lithium-ion electricity of low cation mixing
Pond positive electrode and preparation method thereof.
Background technology
With the development of ev industry, power lithium-ion battery demand constantly increases.However, lithium ion power is electric
Pond is higher to the requirement in terms of the capacity of battery material, security and cyclicity.At present, the LiFePO4 of in the market and common
Ternary lithium ion battery battery material has been increasingly difficult to meet the requirement of electrokinetic cell, needs badly and develops new lithium ion battery
Positive electrode.
Nickelic lithium ion battery material is high because of capacity, and price properly and is widely paid close attention to, and is also described as the next generation most
One of important power lithium-ion battery positive electrode.However, the nickel content of nickelic anode material for lithium-ion batteries is high, bar is prepared
Part is extremely harsh.In sintering preparation process, it is difficult to by the nickel ion complete oxidation of substantial amounts of+2 valency, cause in material in the presence of scarce
Fall into, especially show that the cation mixing degree in material crystal structure is high, the chemical property of material declines, and governs the material
Further development and application.Therefore the nickelic anode material for lithium-ion batteries of low cation mixing is developed, and then improves material
Cycle performance be current power ion battery market active demand and research Hot Contents.
The content of the invention
In order to solve the above problems, the present invention develops that " presoma mixes lithium the pre-heat treatment-oxygen-enriched high-temperature roasting-low temperature and moved back
The nickelic anode material for lithium-ion batteries synthesis technique of fire ".This method is simple to operate, equipment requirement is low, be easy to market-oriented popularization,
Wide market.
To achieve these goals, the invention provides a kind of low nickelic ball-shaped lithium-ion battery anode material of cation mixing
The preparation method of material, including by chemical formula be NixCoyMn1-x-y(OH)2Nickelic presoma mixed with Li source compound, in advance
The step of heat, heating after preheating, insulation, cooling after insulation, annealing, cooling；Wherein, 0.5<x<1, x+y<1.
The present invention also provides a kind of low nickelic ball-shaped lithium-ion battery anode material of cation mixing, according to previously described
Preparation method is prepared.
By above-mentioned technical proposal, the present invention develops that " presoma mixes lithium the pre-heat treatment-oxygen-enriched high-temperature roasting-low temperature and moved back
The nickelic anode material for lithium-ion batteries synthesis technique of fire ".By the pre-heat treatment, persursor material and lithium salts is set to merge complete；
By oxygen-enriched air roasting, oxidation process makes the nickel ion complete oxidation of low price, it is to avoid dephasign is generated；By process annealing, change
The sequence of kind crystal cationic, makes crystal structure more orderly, lifts the chemical property of material.This method is simple to operate,
Equipment requirement is low, be easy to market-oriented popularization, wide market.Prepare nickelic anode material for lithium-ion batteries have typical case α-
NaFeO2 layer structure, material XRD peak types are complete, and no dephasign generation, crystal face (006) and (102) swarming are obvious, and I (003)/
I(104)>1.2, high-nickel material crystallinity is high, and cation mixing degree is low.Cell testing results are shown, in 1C discharging conditions, material
The discharge capacity first of material is up in more than 160mAh/g, and after circulating 100 times, capacity remains at more than 130mAh/g, display
Good cycle performance.
Other features and advantages of the present invention will be described in detail in subsequent embodiment part.
Brief description of the drawings
Accompanying drawing is, for providing a further understanding of the present invention, and to constitute a part for specification, with following tool
Body embodiment is used to explain the present invention together, but is not construed as limiting the invention.In the accompanying drawings：
Fig. 1 detects shape appearance figure for the ESEM of nickelic lithium anode material made from the embodiment of the present invention 1；
Fig. 2 is the X-ray diffractogram of nickelic lithium anode material made from the embodiment of the present invention 1；
Fig. 3 is the cycle performance curve of nickelic anode material of lithium battery made from the embodiment of the present invention 1；
Fig. 4 is the cycle performance curve of nickelic anode material of lithium battery made from the embodiment of the present invention 2.
Embodiment
The embodiment to the present invention is described in detail below.It should be appreciated that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to limit the invention.
The end points and any value of disclosed scope are not limited to the accurate scope or value herein, these scopes or
Value should be understood to comprising the value close to these scopes or value.For number range, between the endpoint value of each scope, respectively
It can be combined with each other between the endpoint value of individual scope and single point value, and individually between point value and obtain one or more
New number range, these number ranges should be considered as specific open herein.
The invention provides a kind of preparation method of the low nickelic ball-shaped lithium-ion battery anode material of cation mixing, including
It is Ni by chemical formulaxCoyMn1-x-y(OH)2Nickelic presoma mixed with Li source compound, preheat, after preheating heat up, protect
The step of temperature, cooling after insulation, annealing, cooling；Wherein 0.5<x<1, x+y<1.
In the above-mentioned technical solutions, chemical formula is NixCoyMn1-x-y(OH)2Nickelic presoma, wherein, 0.5<x<1, x+
y<1, it can be prepared by a variety of methods, for example, by mixed solution and precipitant solution containing nickel salt, cobalt salt and manganese salt
Reacted in the solution containing complexing agent, filter, by drying precipitate, obtain presoma, wherein, nickel salt, cobalt salt and manganese salt
Mixed solution in Ni, Co, Mn mol ratio be：x：y：1-x-y, 0.5<x<1, x+y<1.
By above-mentioned technical proposal, the present invention develops that " presoma mixes lithium the pre-heat treatment-oxygen-enriched high-temperature roasting-low temperature and moved back
The nickelic anode material for lithium-ion batteries synthesis technique of fire ".By the pre-heat treatment, persursor material and lithium salts is set to merge complete；
By oxygen-enriched air roasting, oxidation process makes the nickel ion complete oxidation of low price, it is to avoid dephasign is generated；By process annealing, change
The sequence of kind crystal cationic, makes crystal structure more orderly, lifts the chemical property of material.This method is simple to operate,
Equipment requirement is low, be easy to market-oriented popularization, wide market.Prepare nickelic anode material for lithium-ion batteries have typical case α-
NaFeO2 layer structure, material XRD peak types are complete, and no dephasign generation, crystal face (006) and (102) swarming are obvious, and I (003)/
I(104)>1.2, high-nickel material crystallinity is high, and cation mixing degree is low.Cell testing results are shown, in 1C discharging conditions, material
The discharge capacity first of material is up in more than 160mAh/g, and after circulating 100 times, capacity remains at more than 130mAh/g, display
Good cycle performance.
In the above-mentioned technical solutions, in nickelic presoma in total amount and Li source compound containing Ni, Co and Mn Li mole
Than that can have multiple choices, in order to obtain the cell positive material that Ni, Co and Mn and Li content ratios and anticipation ratio match,
Preferably, Li mol ratio is in total amount and Li source compound containing Ni, Co and Mn in nickelic presoma：1:1.04~1.06.
In the above-mentioned technical solutions, nickel presoma can have multiple choices with Li source compound hybrid mode, in order to obtain
The cell positive material that Ni, Co and Mn and Li content ratios and anticipation ratio match, it is preferable that nickelic presoma and lithium source
Compound hybrid mode stirs for grinding.
In the above-mentioned technical solutions, Li source compound can have multiple choices, in order to obtain Ni, Co and Mn and Li contents
The cell positive material that ratio and anticipation ratio match, it is preferable that Li source compound is lithium carbonate, lithium acetate, lithium oxalate, phosphorus
One or more in sour lithium, lithium nitrate and lithium chloride.
In the above-mentioned technical solutions, the hybrid mode of nickelic presoma and Li source compound has multiple choices, in order to obtain
The cell positive material that Ni, Co and Mn and Li content ratios and anticipation ratio match, it is preferable that hybrid mode is stirred for grinding
Mix, incorporation time is 10-20min.
In the above-mentioned technical solutions, preheating condition can be adjusted in relative broad range, in order that persursor material and lithium salts melt
Close complete, it is preferable that preheating temperature is 300~600 DEG C.
Preheating time can adjust in relative broad range, in order that persursor material and lithium salts fusion are complete, further,
Preheating time is 3~6 hours.
Preheating atmosphere can be adjusted in relative broad range, in order that persursor material and lithium salts fusion are complete, further,
Atmospheric condition is air atmosphere.
In the above-mentioned technical solutions, heat-retaining condition can be adjusted in relative broad range, for oxidation process, make low price
Nickel ion complete oxidation, it is to avoid dephasign is generated, it is preferable that holding temperature is 700~950 DEG C.
In the above-mentioned technical solutions, soaking time can be adjusted in relative broad range, for oxidation process, make low price
Nickel ion complete oxidation, it is to avoid dephasign is generated, it is preferable that soaking time is 15~20 hours.
In the above-mentioned technical solutions, insulation atmosphere can be adjusted in relative broad range, for oxidation process, make low price
Nickel ion complete oxidation, it is to avoid dephasign is generated, it is preferable that insulation atmosphere is oxygen atmosphere.Further, for oxidation
Process, makes the nickel ion complete oxidation of low price, it is to avoid dephasign is generated, and the concentration of oxygen is not less than 85%.
In the above-mentioned technical solutions, heating rate can be adjusted in relative broad range after preheating, excellent in order to avoid dephasign is generated
Heating rate is 8~10 DEG C/min after selection of land, preheating.
In the above-mentioned technical solutions, rate of temperature fall can be adjusted in relative broad range after insulation, for oxidation process, be kept away
Exempt from dephasign generation, it is preferable that rate of temperature fall is 8~10 DEG C/min after insulation.
In the above-mentioned technical solutions, the type of cooling can have multiple choices, in order that crystal structure is more orderly, preferably
Ground, the type of cooling is natural cooling.
In the above-mentioned technical solutions, annealing conditions can be adjusted in relative broad range, in order to improve the row of crystal cationic
Sequence, makes crystal structure more orderly, lifts the chemical property of material, it is preferable that annealing temperature is 400~600 DEG C.
In the above-mentioned technical solutions, annealing time can be adjusted in relative broad range, in order to improve the row of crystal cationic
Sequence, makes crystal structure more orderly, lifts the chemical property of material, it is preferable that annealing time is 20~30 hours.
In the above-mentioned technical solutions, annealing atmosphere can be adjusted in relative broad range, in order to improve the row of crystal cationic
Sequence, makes crystal structure more orderly, lifts the chemical property of material, it is preferable that annealing atmosphere is oxygen atmosphere.
In the above-mentioned technical solutions, the concentration of oxygen can be adjusted in relative broad range, in order to improve crystal cationic
Sequence, makes crystal structure more orderly, lifts the chemical property of material, further, and the concentration of oxygen is not less than 85%.
The present invention also provides a kind of low nickelic ball-shaped lithium-ion battery anode material of cation mixing, according to previously described
Preparation method is prepared.
Pass through above-mentioned technical proposal, the nickel ion complete oxidation of low price of the present invention, it is to avoid dephasign is generated, improve crystal middle-jiao yang, function of the spleen and stomach
The sequence of ion, makes crystal structure more orderly, and the chemical property high-nickel material crystallinity for lifting material is high, cation mixing
Degree is low.
Further, the chemical formula of nickelic lithium ion battery material described previously is LiNixCoyMn1-x-yO2, wherein,
0.5<x<1, x+y<1.
Moreover, nickelic lithium ion battery material described previously is spheric granules, and average grain diameter is 9~12 microns, tool
There are typical α-NaFeO2Layer structure.
By above-mentioned technical proposal, the present invention develops that " presoma mixes lithium the pre-heat treatment-oxygen-enriched high-temperature roasting-low temperature and moved back
The nickelic anode material for lithium-ion batteries synthesis technique of fire ".By the pre-heat treatment, persursor material and lithium salts is set to merge complete；
By oxygen-enriched air roasting, oxidation process makes the nickel ion complete oxidation of low price, it is to avoid dephasign is generated；By process annealing, change
The sequence of kind crystal cationic, makes crystal structure more orderly, lifts the chemical property of material.This method is simple to operate,
Equipment requirement is low, be easy to market-oriented popularization, wide market.Prepare nickelic anode material for lithium-ion batteries have typical case α-
NaFeO2 layer structure, material XRD peak types are complete, and no dephasign generation, crystal face (006) and (102) swarming are obvious, and I (003)/
I(104)>1.2, high-nickel material crystallinity is high, and cation mixing degree is low.Cell testing results are shown, in 1C discharging conditions, material
The discharge capacity first of material is up in more than 160mAh/g, and after circulating 100 times, capacity remains at more than 130mAh/g, display
Good cycle performance.
The present invention will be described in detail by way of examples below.
Embodiment 1
It is Ni by chemical formula0.8Co0.1Mn0.1(OH)2Nickelic presoma and lithium carbonate powder, wherein, in nickelic presoma
Li mol ratio is in total amount and lithium carbonate containing Ni, Co and Mn：1:1.05, by the two grinding stirring 10min；Again at 450 DEG C,
5h is preheated, wherein atmospheric condition is air atmosphere；After preheating terminates, using heating rate as 9 DEG C/min, 800 DEG C, guarantor are warming up to
Temperature 18 hours, insulation atmosphere is oxygen atmosphere, and the concentration of oxygen is 85%, and rate of temperature fall is 10 DEG C/min after insulation, is cooled to
600 DEG C, anneal 15 hours, annealing atmosphere is oxygen atmosphere, and the concentration of oxygen is 85%, after annealing terminates, naturally cools to room
Warm (20 DEG C).
The content of nickel cobalt manganese lithium in the present embodiment is tested using Atomic absorption, its atom number is Li：Ni： Co：Mn=
1.003:0.8:0.0992:0.105, obtained product atom number is more consistent than with the ratio in designing material.
Fig. 1 is the SEM image of obtained material in the present embodiment.It can be found that it is spheric granules group that material, which is made, from Fig. 1
Aggressiveness, even particle size distribution, graininess is good, and particle diameter is between 9~12 microns, with preferable processing characteristics.
Fig. 2 is the XRD that material is made, from Fig. 2 it can be found that cell positive material has typical case α-NaFeO2 stratiform
Structure, material XRD peak types are complete, and no dephasign generation, crystal face (006) and (102) swarming are obvious, I (003)/I (104)>1.2
(referring to Fig. 2), shows the high-nickel material crystallinity height prepared using the method for exploitation, and cation mixing degree is low, successfully prepares
The nickel lithium manganate cathode material of pure phase.
The positive electrode that the present embodiment is prepared is 8 according to mass ratio with acetylene black, Kynoar (PVDF):1:
1 ratio uniform mixing, is then pressed into piece using tablet press machine, then a diameter of 6mm thin slice is made with the mode of punching, obtains
The thin slice arrived is dried in vacuo 12 hours under the conditions of 100 DEG C, and electrode slice is made；Using 1mol/L LIPF6 as electrolyte, polypropylene
Microporous barrier (Celgard2400) is barrier film, and metal lithium sheet is reference electrode, and material is made in the glove box full of hydrogen
CR2032 type button cells.Under the conditions of 25 DEG C, the Land-CT2001A battery test system make-ups of Wuhan Lan electricity companies are utilized
Formula battery carries out constant current charge-discharge test, and test voltage scope is 2.7V~4.3V.
Fig. 3 be button cell made from the present embodiment under the conditions of 1C discharge and recharges, the cycle performance curve map of material.From figure
3 it can be found that the first discharge specific capacity of the material is after 170mAh/g or so, 100 circulations, and capacity is remained at
More than 150mAh/g, good cycle.
Embodiment 2
It is Ni by chemical formula0.6Co0.2Mn0.2(OH)2Nickelic presoma and lithium carbonate powder, wherein, in nickelic presoma
Li mol ratio is in total amount and lithium carbonate containing Ni, Co and Mn：1:1.04, by the two grinding stirring 20min；Again at 300 DEG C,
3h is preheated, wherein atmospheric condition is air atmosphere；After preheating terminates, using heating rate as 8 DEG C/min, 700 DEG C, guarantor are warming up to
Temperature 15 hours, insulation atmosphere is oxygen atmosphere, and the concentration of oxygen is 90%, and rate of temperature fall is 8 DEG C/min after insulation, is cooled to
400 DEG C, anneal 20 hours, annealing atmosphere is oxygen atmosphere, and the concentration of oxygen is 90%, after annealing terminates, naturally cools to room
Warm (20 DEG C).
The content of nickel cobalt manganese lithium in the present embodiment is tested using Atomic absorption, its atom number is Li：Ni： Co：Mn=
1.005:0.6:0.1991:0.204, obtained product atom number is more consistent than with the ratio in designing material.
It is consistent in scanned Electronic Speculum detection and X diffraction ray detections, testing result and embodiment 1.
The positive electrode that the present embodiment is prepared is 8 according to mass ratio with acetylene black, Kynoar (PTFE):1:
1 ratio uniform mixing, is then pressed into piece using tablet press machine, then a diameter of 6mm thin slice is made with the mode of punching, obtains
The thin slice arrived is dried in vacuo 12 hours under the conditions of 100 DEG C, and electrode slice is made；Using 1mol/L LIPF6 as electrolyte, polypropylene
Microporous barrier (Celgard2400) is barrier film, and metal lithium sheet is reference electrode, and material is made in the glove box full of hydrogen
CR2032 type button cells.Under the conditions of 25 DEG C, the Land-CT2001A battery test system make-ups of Wuhan Lan electricity companies are utilized
Formula battery carries out constant current charge-discharge test, and test voltage scope is 2.7V~4.3V.
Fig. 4 be button cell made from the present embodiment under the conditions of 1C discharge and recharges, the cycle performance curve map of material.From figure
4 it can be found that the first discharge specific capacity of the material is after more than 160mAh/g, 100 circulations, and capacity is remained at
More than 140mAh/g, good cycle.
Embodiment 3
It is Ni by chemical formula0.7Co0.1Mn0.2(OH)2Nickelic presoma and lithium carbonate powder, wherein, in nickelic presoma
Li mol ratio is in total amount and lithium carbonate containing Ni, Co and Mn：1:1.06, by the two grinding stirring 15min；Again at 600 DEG C,
6h is preheated, wherein atmospheric condition is air atmosphere；After preheating terminates, using heating rate as 10 DEG C/min, 950 DEG C are warming up to,
Insulation 20 hours, insulation atmosphere is oxygen atmosphere, and the concentration of oxygen is 95%, and rate of temperature fall is 10 DEG C/min after insulation, cooling
To 600 DEG C, anneal 30 hours, annealing atmosphere is oxygen atmosphere, and the concentration of oxygen is 95%, after annealing terminates, is naturally cooled to
Room temperature (20 DEG C).
After testing, obtained product atom number is more consistent than with the ratio in designing material.Scanned Electronic Speculum detection and X spread out
Penetrate consistent in ray detection, testing result and embodiment 1.
Embodiment 4
The low nickelic ball-shaped lithium-ion battery anode material of cation mixing is prepared according to the preparation method in embodiment 1, no
It is both that the chemical formula of nickelic presoma is Ni0.6Co0.3Mn0.1(OH)2。
Similarly, after testing, obtained product atom number is more consistent than with the ratio in designing material.To the button electricity being made
Pond carries out constant current charge-discharge test, and test voltage scope is 2.7V~4.3V, and good cycle.
After testing, obtained product atom number is more consistent than with the ratio in designing material.Scanned Electronic Speculum detection and X spread out
Penetrate consistent in ray detection, testing result and embodiment 1.
Embodiment 5
The low nickelic ball-shaped lithium-ion battery anode material of cation mixing is prepared according to the preparation method in embodiment 1, no
It is both that the chemical formula of nickelic presoma is Ni0.6Co0.2Mn0.2(OH)2。
Similarly, after testing, obtained product atom number is more consistent than with the ratio in designing material.To the button electricity being made
Pond carries out constant current charge-discharge test, and test voltage scope is 2.7V~4.3V, and good cycle.
After testing, obtained product atom number is more consistent than with the ratio in designing material.Scanned Electronic Speculum detection and X spread out
Penetrate consistent in ray detection, testing result and embodiment 1.
Embodiment 6
The low nickelic ball-shaped lithium-ion battery anode material of cation mixing is prepared according to the preparation method in embodiment 1, no
It is both that lithium carbonate is replaced with lithium acetate.
Similarly, after testing, obtained product atom number is more consistent than with the ratio in designing material.To the button electricity being made
Pond carries out constant current charge-discharge test, and test voltage scope is 2.7V~4.3V, and good cycle.
After testing, obtained product atom number is more consistent than with the ratio in designing material.Scanned Electronic Speculum detection and X spread out
Penetrate consistent in ray detection, testing result and embodiment 1.
Embodiment 7
The low nickelic ball-shaped lithium-ion battery anode material of cation mixing is prepared according to the preparation method in embodiment 1, no
It is both that lithium carbonate is replaced with lithium oxalate.
Similarly, after testing, obtained product atom number is more consistent than with the ratio in designing material.To the button electricity being made
Pond carries out constant current charge-discharge test, and test voltage scope is 2.7V~4.3V, and good cycle.
After testing, obtained product atom number is more consistent than with the ratio in designing material.Scanned Electronic Speculum detection and X spread out
Penetrate consistent in ray detection, testing result and embodiment 1.
The preferred embodiment of the present invention described in detail above, still, the present invention are not limited in above-mentioned embodiment
Detail, in the range of the technology design of the present invention, a variety of simple variants can be carried out to technical scheme, this
A little simple variants belong to protection scope of the present invention.
It is further to note that each particular technique feature described in above-mentioned embodiment, in not lance
In the case of shield, can be combined by any suitable means, in order to avoid unnecessary repetition, the present invention to it is various can
The combination of energy no longer separately illustrates.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should equally be considered as content disclosed in this invention.
Claims (10)
1. a kind of preparation method of the low nickelic ball-shaped lithium-ion battery anode material of cation mixing, it is characterised in that including inciting somebody to action
Chemical formula is NixCoyMn1-x-y(OH)2Nickelic presoma mixed with Li source compound, preheat, after preheating heat up, insulation,
The step of cooling after insulation, annealing, cooling；
Wherein, 0.5<x<1, x+y<1.
2. preparation method according to claim 1, wherein, total amount and lithium source containing Ni, Co and Mn in nickelic presoma
Li mol ratio is in compound：1:1.04~1.06.
3. preparation method according to claim 1, wherein, nickelic presoma is stirred with Li source compound hybrid mode for grinding
Mix.
4. preparation method according to claim 1, wherein, Li source compound is lithium carbonate, lithium acetate, lithium oxalate, phosphoric acid
One or more in lithium, lithium nitrate and lithium chloride.
5. preparation method according to claim 1, wherein, incorporation time is 10-20min.
6. preparation method according to claim 1, wherein, preheating condition includes：Preheating temperature is 300~600 DEG C；With/
Or, preheating time is 3~6 hours；And/or, atmospheric condition is air atmosphere.
7. preparation method according to claim 1, wherein, heat-retaining condition includes：Temperature is 700~950 DEG C；And/or, protect
The warm time is 15~20 hours；And/or, insulation atmosphere is oxygen atmosphere, it is preferable that the concentration of oxygen is not less than 85%.
8. preparation method according to claim 1, wherein, heating rate is 8~10 DEG C/min after preheating；And/or, insulation
Rate of temperature fall is 8~10 DEG C/min afterwards；And/or, the type of cooling is natural cooling.
9. preparation method according to claim 1, wherein, annealing conditions include：Temperature is 400~600 DEG C；And/or, move back
The fiery time is 20~30 hours；And/or, annealing atmosphere is oxygen atmosphere, it is preferable that the concentration of oxygen is not less than 85%.
10. a kind of low nickelic ball-shaped lithium-ion battery anode material of cation mixing, it is characterised in that according to claim 1-9
Any described preparation method is prepared；
Preferably, the chemical formula of the nickelic lithium ion battery material is LiNixCoyMn1-x-yO2, wherein, 0.5<x<1, x+y<1；
And/or, the material is spheric granules, and average grain diameter is 9~12 microns, with typical α-NaFeO2Layer structure.
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| CN108346797A (en) * | 2018-03-13 | 2018-07-31 | 昶联金属材料应用制品(广州)有限公司 | The preparation method of nickelic ternary material |
| CN108493435A (en) * | 2018-05-31 | 2018-09-04 | 电子科技大学 | Anode material for lithium-ion batteries Li (Ni0.8Co0.1Mn0.1)1-xYxO2And preparation method |
| CN109406554A (en) * | 2018-10-12 | 2019-03-01 | 圣戈莱（北京）科技有限公司 | A kind of method for qualitative analysis of tertiary cathode material chemical property |
| CN111217407A (en) * | 2020-01-16 | 2020-06-02 | 东莞东阳光科研发有限公司 | High-nickel anode material and preparation method and application thereof |
| CN112436134A (en) * | 2019-04-28 | 2021-03-02 | 宁德时代新能源科技股份有限公司 | Positive electrode active material, preparation method thereof, positive electrode plate, lithium ion secondary battery and electric vehicle |
| CN113629254A (en) * | 2021-10-12 | 2021-11-09 | 浙江帕瓦新能源股份有限公司 | Preparation method of single crystal high-nickel low-cobalt or cobalt-free cathode material |
| CN115974171A (en) * | 2022-09-29 | 2023-04-18 | 宁夏汉尧富锂科技有限责任公司 | Cathode material prepared by wet lithium-poor process and preparation method thereof |
| CN117594789A (en) * | 2024-01-18 | 2024-02-23 | 四川新能源汽车创新中心有限公司 | High-nickel ternary positive electrode material, preparation method thereof, lithium ion battery and electric equipment |
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| CN115974171A (en) * | 2022-09-29 | 2023-04-18 | 宁夏汉尧富锂科技有限责任公司 | Cathode material prepared by wet lithium-poor process and preparation method thereof |
| CN117594789A (en) * | 2024-01-18 | 2024-02-23 | 四川新能源汽车创新中心有限公司 | High-nickel ternary positive electrode material, preparation method thereof, lithium ion battery and electric equipment |
| CN117594789B (en) * | 2024-01-18 | 2024-04-16 | 四川新能源汽车创新中心有限公司 | High-nickel ternary positive electrode material, preparation method thereof, lithium ion battery and electric equipment |
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