CN108598379A - A kind of tungstate lithium cladding nickel cobalt aluminic acid lithium composite material and its preparation method and application - Google Patents
A kind of tungstate lithium cladding nickel cobalt aluminic acid lithium composite material and its preparation method and application Download PDFInfo
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Abstract
The invention discloses a kind of tungstate lithiums to coat nickel cobalt aluminic acid lithium composite material and its preparation method and application, and nickel cobalt aluminium precursor is scattered in lithium-containing solution, adds three cobalt oxides, and lithium-containing solution will be reacted with three cobalt oxides generates Li2WO4, in evaporation and crystal process, Li2WO4Cladding will be deposited directly on nickel cobalt aluminium presoma, then be carried out mixed lithium and be sintered up to LiNi0.8Co0.15Al0.05O2@Li2WO4, by this reaction in-situ, it is formed by deposition cladding, highly uniform clad can be formed.In addition the present invention is coated by crystallization deposition, gained clad good crystallinity, uniform component；It is applied in lithium ion battery as tertiary cathode material, gained cycle performance of lithium ion battery is stablized, and high rate performance is excellent.
Description
Technical field
The present invention relates to a kind of tungstate lithiums to coat nickel cobalt aluminic acid lithium composite material and its preparation method and application, belong to lithium from
Sub- battery material field.
Background technology
Currently, lithium ion battery has been widely used for various portable electronic products, electric tool and energy-storage system.
In the case that global energy and environmental problem are increasingly severeer, lithium ion battery is by mobile phone, laptop, digital camera and just
Formula compact electric apparatus is taken, electric powered motor field, therefore the cycle performance to lithium ion battery, energy density and peace are gradually moved towards
Higher requirements are also raised for full performance.Ternary material has played the synergistic effect of nickel cobalt manganese or nickel cobalt aluminium, thus performance it is good
In one-component layered cathode material, and it is considered as one of the novel anode material for most having application prospect.
The study found that for tertiary cathode material, with the increase of nickel content in material, the active oxygen of material surface
Ion can and air in carbon dioxide generate carbonate, then with the residual lithium on surface and move to material surface lithium ion it is anti-
Lithium carbonate should be generated.So that material surface alkalinity is crossed high water absorption, influences processing and the storage performance of material, in addition to this, electrolyte
In containing a certain amount of HF can with positive electrode occur side reaction.In order to improve this situation, domestic and international producer mainly uses water
It washes or carries out oxide coated, fluoride, phosphate etc. on positive electrode surface.Washing can substantially reduce the capacity of material and follow
Ring performance, and material is oxide coated, fluoride, phosphate, these coatings are free of lithium ion, in lithium ion deintercalation process
It is middle to play the role of obstruction, it is unfavorable for the transmission of lithium ion.
Invention content
In view of the deficiencies of the prior art, of the invention first is designed to provide a kind of wolframic acid with uniform clad
Lithium coats nickel cobalt aluminic acid lithium composite material.
Second object of the present invention is to provide a kind of continuous high-efficient, low-cost tungstate lithium in-stiu coating nickel cobalt aluminium
The preparation method of sour lithium composite material.
Third object of the present invention is to provide a kind of tungstate lithium and coats nickel cobalt aluminic acid lithium composite material in lithium-ion electric
Application in pond.Gained lithium ion battery has stable cycle performance and excellent high rate performance.
A kind of tungstate lithium of the present invention coats nickel cobalt aluminic acid lithium composite material, and the composite material is by core material and clad
It constitutes, the core material is nickel cobalt lithium aluminate, chemical formula LiNi0.8Co0.15Al0.05O2, the clad is tungstate lithium
(Li2WO4)。
Preferred scheme, in the composite material, the mass fraction of clad is 0.1%~5wt%.As further
It is preferred that in the composite material, the mass fraction of clad is 1%~2wt%.
A kind of preparation method of tungstate lithium cladding nickel cobalt aluminic acid lithium composite material of the present invention, includes the following steps：
By nickel cobalt aluminium (Ni0.8Co0.15Al0.05(OH)2) presoma be added lithium-containing solution in be uniformly mixed obtain slurries A, to
Tungstic acid is added in slurries A and is uniformly mixed acquisition slurries B, slurries B is evaporated and crystallizes to slurries B dryings, is crystallized
Product carries out mixed lithium sintering to crystallized product under an oxygen-containing atmosphere, that is, obtains tungstate lithium and coat nickel cobalt lithium aluminate
(LiNi0.8Co0.15Al0.05O2@Li2WO4) composite material；
In the slurries B, the quality of tungstic acid is the 0.1%~5% of nickel cobalt aluminium precursor quality.
In the inventive solutions, nickel cobalt aluminium precursor is scattered in lithium-containing solution, adds three cobalt oxides, contains
Lithium solution will be reacted with three cobalt oxides generates Li2WO4, in evaporation and crystal process, Li2WO4It will be directly on nickel cobalt aluminium presoma
Deposition cladding, then carry out mixed lithium and be sintered up to Li2WO4The LiNi of cladding0.8Co0.15Al0.05O2, this reaction in-situ is formed by
Deposition cladding, can form highly uniform clad.
Preferred scheme, the lithium-containing solution are Lithium carbonate solution or lithium hydroxide solution, the concentration of the lithium-containing solution
≥0.01mol/L.As a further preference, a concentration of 0.2~1mol/L of the lithium-containing solution.
Preferred scheme, in the slurries A, liquid-solid ratio is 5~30:1.As a further preference, in the slurries A,
Liquid-solid ratio is 10~20:1.
Preferred scheme, in the slurries B, the quality of tungstic acid is the 1%~2% of nickel cobalt aluminium precursor quality.
Preferred scheme, the lithium source in the mixed lithium sintering are selected from lithium hydroxide, lithium carbonate, lithium nitrate, lithium oxalate, acetic acid
Any one in lithium.As a further preference, the lithium source in the mixed lithium sintering is lithium hydroxide.
The temperature of preferred scheme, the evaporative crystallization is 80~100 DEG C
Preferred scheme mixes elemental lithium (Li) in the material after lithium：The sum of nickel element and cobalt element, aluminium element (Ni+Co+
Al molar ratio) is 1.01~1.15：1.
As a further preference, it mixes in the material after lithium, Li：(Ni+Co+Al) molar ratio is 1.03~1.05:1.
The temperature of preferred scheme, the sintering is 700 DEG C~800 DEG C, and the time of the sintering is 8~20h.
Preferred scheme, the oxygen-containing atmosphere are oxygen atmosphere or air atmosphere.
In the present invention, the nickel cobalt aluminium forerunner preparation is：According to the chemical formula of nickel cobalt lithium aluminate based on chemistry
Amount is than respectively with nickel source, cobalt source, silicon source formation mixed solution soluble in water is taken, by mixed solution and ammonium hydroxide, sodium hydroxide solution
Reaction kettle is added in cocurrent, reaction product is obtained after reaction, washed is nickel cobalt aluminium presoma.
Preferred scheme, any one of the nickel source in nickel sulfate, nickel chloride, nickel oxalate, nickel acetate, the cobalt
Any one of source in cobaltous sulfate, cobalt chloride, cobalt oxalate, cobalt acetate, source of aluminium are selected from aluminum sulfate, aluminium chloride, oxalic acid
Any one in aluminium, aluminum acetate.
Preferred scheme, in the mixed solution, a concentration of 1mol/L~4mol/L of (Ni+Co+Al).
Preferred scheme, Nong Du Wei≤1mol/L of the ammonium hydroxide.
Preferred scheme, a concentration of 1~15mol/L of the sodium hydroxide solution.
Preferred scheme, in the reaction kettle, the temperature of reaction is 45~60 DEG C, and the time of reaction is 5~65h.
In the preparation process of nickel cobalt aluminium presoma, controlling pH in reaction kettle by the addition of ammonium hydroxide and sodium hydroxide is
10.3~10.4, and control a concentration of 8g/L~9g/L of ammonium root.
A kind of application of tungstate lithium cladding nickel cobalt aluminic acid lithium composite material of the present invention, tungstate lithium cladding nickel cobalt lithium aluminate is answered
Condensation material is applied to as anode material for lithium-ion batteries in lithium ion battery.
The principle of the present invention and advantage：
It in the prior art, typically will be before nickel cobalt lithium aluminate or nickel cobalt aluminium when carrying out nickel cobalt lithium aluminate coating modification
Drive body is directly mixed with modified material to be re-sintered, and the mode of this mixing, which is formed by clad, to be formed inside core material
Whole uniform cladding, and the cladding form on only a kind of surface.
And technical scheme of the present invention, can directly it be occurred with tungstic acid using lithium hydroxide or Lithium carbonate solution anti-
It answers, generates Li2WO4The characteristics of, nickel cobalt aluminium presoma is scattered in lithium-containing solution, after tungstic acid is added, lithium-containing solution and three
Tungsten oxide reaction generates Li2WO4, cladding is deposited directly on nickel cobalt aluminium presoma during evaporative crystallization, then mixed lithium is burnt
Knot obtains Li2WO4The LiNi of coating modification0.8Co0.15Al0.05O2.By this reaction in-situ, it is formed by deposition cladding, it can be with
Form highly uniform clad.In addition the present invention is coated by crystallization deposition, gained clad good crystallinity, uniform component.
Preparation method through the invention simultaneously, can high-volume modification nickel cobalt aluminium presoma, technique is continuously simple
It is of low cost.
In the present invention, raw material tungstic acid used is common raw material in industry, the lithium carbonate or hydrogen-oxygen in addition used
It is convenient source, low cost of raw materials to change lithium also.
In the present invention, gained LiNi0.8Co0.15Al0.05O2@Li2WO4Composite material, clad good crystallinity, ingredient are equal
One, it is applied in lithium ion battery as tertiary cathode material, gained cycle performance of lithium ion battery is stablized, high rate performance
It is excellent.
Tungstate lithium cladding nickel cobalt aluminic acid lithium composite material technique of the present invention is continuous, and treating capacity flexibility and changeability has wide
Industrial applications foreground.
Description of the drawings
【Fig. 1】It is followed under 0.2C (1C=180mAh/g) current density for unmodified sample, embodiment 1,2,3 and comparative example 1
Ring performance map；
【Fig. 2】For the high rate performance figure of unmodified sample, embodiment 1,2,3 and comparative example 1 under different current densities；
【Fig. 3】The SEM figures that Fig. 3 (a) is unmodified sample, Fig. 3 (b) is embodiment 1.
Specific implementation mode
Following embodiment is intended to be described in further details the content of present invention；And the protection domain of the claims in the present invention
It is not limited by the example.
In the following Examples and Comparative Examples, the preparation of nickel cobalt aluminium presoma is as follows：
By nickel sulfate, cobaltous sulfate, aluminum sulfate according to 0.8:0.15:0.05 proportional arrangement is at mixing salt solution, salt-mixture
The concentration 2mol/L of (Ni+Co+Al) in solution, by mixing salt solution with the ammonium hydroxide of the flow of 100ml/min and 7.5mol/L；
7.5mol/L sodium hydroxide solution；, cocurrent be added 100L reaction kettles in, control reaction kettle in PH be 10.3~10.4, ammonium root is dense
Degree is that 8g/L~9g/L reacts 50h under 55 DEG C of temperature conditions；Gained precipitates, to get nickel cobalt aluminium forerunner after filtration washing 3 times
Body.
Embodiment 1
By nickel cobalt aluminium presoma 100g, the lithium hydroxide solution of a concentration of 1mol/L of 1L is added, stirring at low speed is uniformly mixed
Obtain liquid A, after the tungstic acid of nickel cobalt aluminium forerunner weight 1% be added thereto obtain slurries B；Slurries B is carried out 90
Evaporative crystallization to slurries are dried at DEG C, then gained crystallized product is carried out mixed lithium, are mixed into lithium hydroxide, are mixed in the material after lithium,
Li：(Ni+Co+Al) molar ratio is 1.05, and the material after mixed lithium is then sintered 15h in oxygen at a temperature of 750 DEG C to obtain the final product
LiNi0.8Co0.15Al0.05O2@Li2WO4Composite material.
Li in the present embodiment2WO4Clad is in LiNi0.8Co0.15Al0.05O2@Li2WO4The mass fraction of composite material is
1%.
The LiNi obtained using the present embodiment0.8Co0.15Al0.05O2@Li2WO4In 0.2C (1C=180mAh/g) current density
Under cycle performance such as Fig. 1, high rate performance such as Fig. 2.
From figure 1 it appears that under 0.2C current densities, initial discharge specific capacity is 187mAh/g, after cycle 50 is enclosed
Specific discharge capacity be 182.1mAh/g, capacity retention ratio 97.4%.
Figure it is seen that under 5C current densities, initial discharge specific capacity is still 150mAh/g.With good times
Rate performance.
Embodiment 2
By nickel cobalt aluminium presoma 200g, the lithium hydroxide solution of a concentration of 1mol/L of 1L is added, stirring at low speed is uniformly mixed
Obtain liquid A, after the tungstic acid of nickel cobalt aluminium forerunner weight 2% be added thereto obtain slurries B；By slurries B at 100 DEG C
Evaporative crystallization to slurries are dried, then gained crystallized product is carried out mixed lithium, are mixed into lithium hydroxide, are mixed in the material after lithium, Li：
(Ni+Co+Al) molar ratio be 1.01, then by the material after mixed lithium in oxygen at a temperature of 700 DEG C be sintered 15h to get
LiNi0.8Co0.15Al0.05O2@Li2WO4Composite material.
Li in the present embodiment2WO4Clad is in LiNi0.8Co0.15Al0.05O2@Li2WO4The mass fraction of composite material is
2%.
The LiNi obtained using the present embodiment0.8Co0.15Al0.05O2@Li2WO4In 0.2C (1C=180mAh/g) current density
Under cycle performance such as Fig. 1, high rate performance such as Fig. 2.
From figure 1 it appears that under 0.2C current densities, initial discharge specific capacity is 181.4mAh/g, 50 circle of cycle
Specific discharge capacity afterwards is 176.9mAh/g, capacity retention ratio 97.2%.
Figure it is seen that under 5C current densities, initial discharge specific capacity is still140.3mAh/g.With good
High rate performance.
Embodiment 3
By nickel cobalt aluminium presoma 100g, the Lithium carbonate solution of a concentration of 0.2mol/L of 1L is added, stirring at low speed is uniformly mixed
Obtain liquid A, after the tungstic acid of nickel cobalt aluminium forerunner weight 1% be added thereto obtain slurries B；By slurries B at 80 DEG C
Evaporative crystallization to slurries are dried, then gained crystallized product is carried out mixed lithium, are mixed into lithium hydroxide, are mixed in the material after lithium, Li：
(Ni+Co+Al) molar ratio be 1.03, then by the material after mixed lithium in oxygen at a temperature of 800 DEG C be sintered 15h to get
LiNi0.8Co0.15Al0.05O2@Li2WO4Composite material.
Li in the present embodiment2WO4Clad is in LiNi0.8Co0.15Al0.05O2@Li2WO4The mass fraction of composite material is
1%.
The LiNi obtained using the present embodiment0.8Co0.15Al0.05O2Following under 0.2C (1C=180mAh/g) current density
Ring performance such as Fig. 1, high rate performance such as Fig. 2.
From figure 1 it appears that under 0.2C current densities, initial discharge specific capacity is 183.5mAh/g, 50 circle of cycle
Specific discharge capacity afterwards is 175.8mAh/g, capacity retention ratio 95.8%.
Figure it is seen that under 5C current densities, initial discharge specific capacity is still 145.2mAh/g.With good
High rate performance.
Comparative example 1
By nickel cobalt aluminium presoma 100g, the lithium hydroxide solution of a concentration of 1mol/L of 1L is added, stirring at low speed is uniformly mixed
Obtain liquid A, after the tungstic acid of nickel cobalt aluminium forerunner weight 8% be added thereto obtain slurries B；Slurries B is evaporated
Crystallization, then products obtained therefrom is subjected to mixed lithium, it is mixed into lithium hydroxide, is mixed in the material after lithium, Li：(Ni+Co+Al) molar ratio is
1.05, then the material after mixed lithium is sintered to 15h in oxygen to get LiNi at a temperature of 750 DEG C0.8Co0.15Al0.05O2@Li2WO4
Composite material.
The LiNi obtained using this comparative example0.8Co0.15Al0.05O2Following under 0.2C (1C=180mAh/g) current density
Ring performance such as Fig. 1, high rate performance such as Fig. 2.
From figure 1 it appears that under 0.2C current densities, initial discharge specific capacity is 174.6mAh/g, 50 circle of cycle
Specific discharge capacity afterwards is 164.3mAh/g, capacity retention ratio 94.1%.
Figure it is seen that under 5C current densities, initial discharge specific capacity is only 112.5mAh/g.
Comparative example 2
By nickel cobalt aluminium presoma 100g, it is uniformly mixed with the tungstate lithium of nickel cobalt aluminium forerunner weight 1.5% and obtains mixture；
Gained mixture carries out mixed lithium, is mixed into lithium hydroxide, mixes in the material after lithium, Li：(Ni+Co+Al) molar ratio is 1.05, so
Afterwards the material after mixed lithium is sintered 15h in oxygen at a temperature of 750 DEG C, obtains LiNi0.8Co0.15Al0.05O2@Li2WO4Composite wood
Material.
By electrochemical property test, under 0.2C current densities, initial discharge specific capacity is 184.7mAh/g, cycle 50
Specific discharge capacity after circle is 172.1mAh/g, capacity retention ratio 93.1%.
Under 5C current densities, initial discharge specific capacity is 132mAh/g.
Comparative example 3
Remaining condition is same as Example 1, only in sintering temperature the scope of the present invention.820 DEG C of sintering 15h in oxygen,
Obtain LiNi0.8Co0.15Al0.05O2@Li2WO4Composite material.
By electrochemical property test, under 0.2C current densities, initial discharge specific capacity is 172.2mAh/g, cycle 50
Specific discharge capacity after circle is 160.1mAh/g, capacity retention ratio 92.9%.
Under 5C current densities, initial discharge specific capacity is 115mAh/g.
Claims (10)
1. a kind of tungstate lithium coats nickel cobalt aluminic acid lithium composite material, it is characterised in that：The composite material is by core material and packet
Coating is constituted, and the core material is nickel cobalt lithium aluminate, chemical formula LiNi0.8Co0.15Al0.05O2, the clad is
Li2WO4。
2. a kind of tungstate lithium according to claim 1 coats nickel cobalt aluminic acid lithium composite material, it is characterised in that：It is described compound
In material, the mass fraction of clad is 0.1%~5wt%.
3. the method for preparing a kind of tungstate lithium cladding nickel cobalt aluminic acid lithium composite material as claimed in claim 1 or 2, feature exist
In：Include the following steps：
Nickel cobalt aluminium presoma is added to be uniformly mixed in lithium-containing solution and obtains slurries A, it is equal that tungstic acid mixing is added into slurries A
Even acquisition slurries B is evaporated slurries B and crystallizes to slurries B dryings, obtains crystallized product, produced under an oxygen-containing atmosphere to crystallization
Object carries out mixed lithium sintering, that is, obtains LiNi0.8Co0.15Al0.05O2@Li2WO4Composite material；
In the slurries B, the quality of tungstic acid is the 0.1%~5% of nickel cobalt aluminium precursor quality.
4. a kind of preparation method of tungstate lithium cladding nickel cobalt aluminic acid lithium composite material according to claim 3, feature exist
In：The lithium-containing solution is Lithium carbonate solution or lithium hydroxide solution, concentration >=0.01mol/L of the lithium-containing solution；It is described
In slurries A, liquid-solid ratio is 5~30：1.
5. a kind of preparation method of tungstate lithium cladding nickel cobalt aluminic acid lithium composite material according to claim 4, feature exist
In：A concentration of 0.2~1mol/L of the lithium-containing solution；In the slurries B, the quality of tungstic acid is nickel cobalt aluminium precursor matter
The 1%~2% of amount.
6. a kind of preparation method of tungstate lithium cladding nickel cobalt aluminic acid lithium composite material according to claim 3, feature exist
In：Any one of lithium source in lithium hydroxide, lithium carbonate, lithium nitrate, lithium acetate in the mixed lithium sintering；After mixed lithium
Li in material：(Ni+Co+Al) molar ratio is 1.01~1.15：1.
7. a kind of preparation method of tungstate lithium cladding nickel cobalt aluminic acid lithium composite material according to claim 3, feature exist
In：The temperature of the sintering is 700 DEG C~800 DEG C, and the time of the sintering is 8~20h.
8. a kind of preparation method of tungstate lithium cladding nickel cobalt aluminic acid lithium composite material according to claim 3, feature exist
In the nickel cobalt aluminium forerunner preparation is：According to the chemical formula of nickel cobalt lithium aluminate stoichiometrically respectively match take nickel source,
Reaction kettle is added, instead in mixed solution and ammonium hydroxide, sodium hydroxide solution cocurrent by cobalt source, silicon source formation mixed solution soluble in water
Should after obtain reaction product, it is washed up to nickel cobalt aluminium presoma.
9. a kind of preparation method of tungstate lithium cladding nickel cobalt aluminic acid lithium composite material according to claim 8, feature exist
In any one of the nickel source in nickel sulfate, nickel chloride, nickel oxalate, nickel acetate, the cobalt source is selected from cobaltous sulfate, chlorine
Change any one in cobalt, cobalt oxalate, cobalt acetate, source of aluminium appointing in aluminum sulfate, aluminium chloride, oxalic acid aluminium, aluminum acetate
Meaning is a kind of；
In the mixed solution, a concentration of 1mol/L~4mol/L of (Ni+Co+Al).
Nong Du Wei≤1mol/L of the ammonium hydroxide.
A concentration of 1~15mol/L of the sodium hydroxide solution.
In the reaction kettle, the temperature of reaction is 45~60 DEG C, and the time of reaction is 5~65h.
10. a kind of application of tungstate lithium cladding nickel cobalt aluminic acid lithium composite material as claimed in claim 1 or 2, it is characterised in that：
Tungstate lithium cladding nickel cobalt aluminic acid lithium composite material described in claim 1~2 is applied in lithium ion battery.
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| CN109879330A (en) * | 2019-02-26 | 2019-06-14 | 哈尔滨工业大学（深圳） | A kind of anode material for lithium-ion batteries and preparation method thereof |
| CN110518221A (en) * | 2019-09-05 | 2019-11-29 | 中南大学 | A kind of method that anti-solvent method prepares lithium metasilicate cladding nickel-cobalt lithium manganate cathode material |
| CN111675251A (en) * | 2020-06-24 | 2020-09-18 | 中航锂电技术研究院有限公司 | Cathode material, preparation method thereof and lithium ion battery |
| CN112349905A (en) * | 2019-08-06 | 2021-02-09 | 湖南杉杉新能源有限公司 | Double-coating modified lithium ion battery positive electrode material and preparation method thereof |
| JP2021048070A (en) * | 2019-09-19 | 2021-03-25 | 住友金属鉱山株式会社 | Positive electrode active material for lithium ion secondary battery and lithium ion secondary battery |
| CN114039031A (en) * | 2021-11-02 | 2022-02-11 | 远景动力技术(江苏)有限公司 | Tungsten single-coating anode material and preparation method and application thereof |
| CN114079043A (en) * | 2020-08-11 | 2022-02-22 | 厦门厦钨新能源材料股份有限公司 | High-nickel positive electrode material, lithium ion battery and preparation method of high-nickel positive electrode material |
| CN116779828A (en) * | 2023-08-16 | 2023-09-19 | 河南科隆新能源股份有限公司 | Preparation method and application of modified sodium ion layered anode material |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103155240A (en) * | 2010-09-30 | 2013-06-12 | 住友金属矿山株式会社 | Positive electrode active material for use in nonaqueous electrolyte secondary cells, manufacturing method thereof, and nonaqueous electrolyte secondary cell using said positive electrode active material |
| CN103339768A (en) * | 2011-02-04 | 2013-10-02 | 丰田自动车株式会社 | Coated active material, battery, and method for producing coated active material |
| CN105336944A (en) * | 2015-12-09 | 2016-02-17 | 四川富骅新能源科技有限公司 | High-capacity cathode material for lithium ion batteries and preparation method thereof |
| CN106654223A (en) * | 2017-01-16 | 2017-05-10 | 北京理工大学 | Modification method for tungsten-containing compound coated positive electrode material of lithium ion battery |
| CN107394172A (en) * | 2017-07-28 | 2017-11-24 | 长安大学 | Tungstate lithium is modified lithium-rich manganese-based layered lithium ion battery positive electrode and preparation method thereof |
-
2018
- 2018-02-08 CN CN201810127974.4A patent/CN108598379A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103155240A (en) * | 2010-09-30 | 2013-06-12 | 住友金属矿山株式会社 | Positive electrode active material for use in nonaqueous electrolyte secondary cells, manufacturing method thereof, and nonaqueous electrolyte secondary cell using said positive electrode active material |
| CN103339768A (en) * | 2011-02-04 | 2013-10-02 | 丰田自动车株式会社 | Coated active material, battery, and method for producing coated active material |
| CN105336944A (en) * | 2015-12-09 | 2016-02-17 | 四川富骅新能源科技有限公司 | High-capacity cathode material for lithium ion batteries and preparation method thereof |
| CN106654223A (en) * | 2017-01-16 | 2017-05-10 | 北京理工大学 | Modification method for tungsten-containing compound coated positive electrode material of lithium ion battery |
| CN107394172A (en) * | 2017-07-28 | 2017-11-24 | 长安大学 | Tungstate lithium is modified lithium-rich manganese-based layered lithium ion battery positive electrode and preparation method thereof |
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| CN112349905B (en) * | 2019-08-06 | 2021-11-23 | 湖南杉杉新能源有限公司 | Double-coating modified lithium ion battery positive electrode material and preparation method thereof |
| CN110518221A (en) * | 2019-09-05 | 2019-11-29 | 中南大学 | A kind of method that anti-solvent method prepares lithium metasilicate cladding nickel-cobalt lithium manganate cathode material |
| CN110518221B (en) * | 2019-09-05 | 2022-04-15 | 中南大学 | Method for preparing lithium silicate coated lithium nickel cobalt manganese oxide positive electrode material by anti-solvent method |
| JP2021048070A (en) * | 2019-09-19 | 2021-03-25 | 住友金属鉱山株式会社 | Positive electrode active material for lithium ion secondary battery and lithium ion secondary battery |
| JP7347061B2 (en) | 2019-09-19 | 2023-09-20 | 住友金属鉱山株式会社 | Positive electrode active material for lithium ion secondary batteries and lithium ion secondary batteries |
| CN111675251A (en) * | 2020-06-24 | 2020-09-18 | 中航锂电技术研究院有限公司 | Cathode material, preparation method thereof and lithium ion battery |
| CN111675251B (en) * | 2020-06-24 | 2022-06-14 | 中创新航技术研究院(江苏)有限公司 | Cathode material, preparation method thereof and lithium ion battery |
| CN114079043A (en) * | 2020-08-11 | 2022-02-22 | 厦门厦钨新能源材料股份有限公司 | High-nickel positive electrode material, lithium ion battery and preparation method of high-nickel positive electrode material |
| CN114039031A (en) * | 2021-11-02 | 2022-02-11 | 远景动力技术(江苏)有限公司 | Tungsten single-coating anode material and preparation method and application thereof |
| CN116779828A (en) * | 2023-08-16 | 2023-09-19 | 河南科隆新能源股份有限公司 | Preparation method and application of modified sodium ion layered anode material |
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