CN102315430B - Preparation method for metallic oxide cladded anode material of lithium ion battery - Google Patents
Preparation method for metallic oxide cladded anode material of lithium ion battery Download PDFInfo
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- CN102315430B CN102315430B CN2011102501576A CN201110250157A CN102315430B CN 102315430 B CN102315430 B CN 102315430B CN 2011102501576 A CN2011102501576 A CN 2011102501576A CN 201110250157 A CN201110250157 A CN 201110250157A CN 102315430 B CN102315430 B CN 102315430B
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- 229910044991 metal oxide Inorganic materials 0.000 title claims abstract description 47
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 29
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 239000010405 anode material Substances 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 10
- 239000000243 solution Substances 0.000 claims description 40
- 239000000843 powder Substances 0.000 claims description 30
- 239000011159 matrix material Substances 0.000 claims description 26
- 150000004706 metal oxides Chemical class 0.000 claims description 22
- 238000003756 stirring Methods 0.000 claims description 22
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 16
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 16
- 239000004094 surface-active agent Substances 0.000 claims description 16
- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical group [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 claims description 12
- 229920000642 polymer Polymers 0.000 claims description 10
- 238000001354 calcination Methods 0.000 claims description 8
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 8
- 229910003002 lithium salt Inorganic materials 0.000 claims description 8
- 159000000002 lithium salts Chemical class 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 239000012266 salt solution Substances 0.000 claims description 8
- 108010010803 Gelatin Proteins 0.000 claims description 7
- 229910013292 LiNiO Inorganic materials 0.000 claims description 7
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 7
- 229920000159 gelatin Polymers 0.000 claims description 7
- 239000008273 gelatin Substances 0.000 claims description 7
- 235000019322 gelatine Nutrition 0.000 claims description 7
- 235000011852 gelatine desserts Nutrition 0.000 claims description 7
- 230000010355 oscillation Effects 0.000 claims description 7
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 6
- 229910012851 LiCoO 2 Inorganic materials 0.000 claims description 6
- 229910013716 LiNi Inorganic materials 0.000 claims description 6
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 229910015645 LiMn Inorganic materials 0.000 claims description 5
- 229910009891 LiAc Inorganic materials 0.000 claims description 4
- 229910010707 LiFePO 4 Inorganic materials 0.000 claims description 4
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 229910013553 LiNO Inorganic materials 0.000 claims description 2
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 2
- 229910006404 SnO 2 Inorganic materials 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 230000031709 bromination Effects 0.000 claims description 2
- 238000005893 bromination reaction Methods 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 239000012467 final product Substances 0.000 claims description 2
- UUFGGXPSBGSYPN-UHFFFAOYSA-N n,n-dimethylmethanamine;hexadecane Chemical compound CN(C)C.CCCCCCCCCCCCCCCC UUFGGXPSBGSYPN-UHFFFAOYSA-N 0.000 claims description 2
- -1 wherein Inorganic materials 0.000 claims 1
- 238000007086 side reaction Methods 0.000 abstract description 4
- 239000000758 substrate Substances 0.000 abstract description 4
- 238000006243 chemical reaction Methods 0.000 abstract description 2
- 238000005253 cladding Methods 0.000 abstract 4
- 230000015271 coagulation Effects 0.000 abstract 2
- 238000005345 coagulation Methods 0.000 abstract 2
- 229940068984 polyvinyl alcohol Drugs 0.000 description 15
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 15
- 238000000576 coating method Methods 0.000 description 12
- 239000011248 coating agent Substances 0.000 description 11
- 239000007788 liquid Substances 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 229910012820 LiCoO Inorganic materials 0.000 description 2
- 238000005354 coacervation Methods 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 description 2
- 229910000000 metal hydroxide Inorganic materials 0.000 description 2
- 150000004692 metal hydroxides Chemical class 0.000 description 2
- 229920002689 polyvinyl acetate Polymers 0.000 description 2
- 239000011149 active material Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 230000009514 concussion Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000001131 transforming effect Effects 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a preparation method for a metallic oxide cladded anode material of a lithium ion battery. According to the method, metallic oxides are cladded over the surface of an anode material substrate by using the method of substrate induced coagulation. The method of substrate induced coagulation is employed in the invention for cladding, which enables cladding of metallic oxides to be uniform and firm, a high cladding rate to be obtained, no side reaction and complete conversion to occur in the process of cladding.
Description
Technical field
The present invention relates to a kind of preparation method of metallic oxide cladded anode material, be specifically related to a kind of preparation method of metallic oxide cladded anode material of lithium ion battery.
Background technology
Along with the fast development of World Economics, the problem of energy shortage and environmental pollution is day by day serious.The exploitation of new forms of energy become one of emphasis of countries in the world scientist research.Wherein, the exploitation of lithium ion battery more and more are subject to world people's attention.Lithium ion battery has been widely used in the power supply of mobile phone, notebook computer, digital camera etc., and progressively substitutes traditional battery in aviation, navigation, space flight and military domain of communication equipment.
Lithium ion battery is comprised of positive electrode, negative material, barrier film and electrolyte.The positive electrode current material mainly contains LiCoO
2, LiMn
2O
4, LiNiO
3, LiNi
xCo
1-xO
2Deng, but all there are different shortcomings in they, can't satisfy people high to the lithium ion battery specific capacity, have extended cycle life, demand that cost is low.Therefore, people are devoted to the study on the modification of anode material for lithium-ion batteries always.At present, a lot of researchers have carried out extensive work, make remarkable progress, and adopt solid phase method or the various clad anode materials of Liquid preparation methods.The surperficial clad material of the people's such as Cao Hui lithium ion cell positive and technique (CN1556551A) propose with e-sol-dipping method, the slaine hydrolysis to be adsorbed onto the positive electrode substrate surface, then roasting become metal oxide.The people's such as Guo Ruisong C and metal oxide coat LiFePO
4Anode material for lithium-ion batteries and preparation method (CN101582495A) propose with C and LSM or CuO coating LiFePO
4, improved powerful chemical property.But said method is adhered to conventional positive electrode surface by only wanting coating by suction-operated, and inhomogeneous, insecure, the wish coating that adsorbs is not more.The metal oxide that is used for coating is transformed by metal hydroxides, has in conversion process side reaction to occur and transform the problems such as incomplete.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of metallic oxide cladded anode material of lithium ion battery, this preparation method adopts and induces coacervation to coat, and metal oxide coats evenly, firmly, clad ratio is high, side reaction can not occur in the coating process, transforms fully.
Above-mentioned purpose of the present invention is achieved by the following technical solution: a kind of preparation method of metallic oxide cladded anode material of lithium ion battery, and adopt matrix to induce coacervation, metal oxide is coated on the surface of positive electrode matrix.
The preparation method of above-mentioned metallic oxide cladded anode material of lithium ion battery specifically contains following steps:
(1) the positive electrode matrix is placed in polymer solution, after stirring, filter and rinsing, obtains powders A;
(2) metal oxide is placed in the lithium salt solution that contains surfactant, after stirring, sonic oscillation, high-speed stirred, get solution B again;
(3) powders A that step (1) is obtained joins in the solution B of step (2) acquisition, after stirring, filtering, then through rinsing, filters and drying, obtains powder C;
(4) with powder C drying, calcining, obtain metallic oxide cladded anode material of lithium ion battery.
In above-mentioned steps:
Positive electrode matrix described in step of the present invention (1) is LiCoO
2, LiMn
2O
4, LiNiO
3, LiNi
xCo
1-xO
2(wherein 0＜x＜1), LiFePO
4Or LiNi
xCo
yM
1-x-yO
2, LiNi
xCo
yM
1-x-yO
2Middle M is Mn, Al, Mg, Ga, Ca, Fe or rare earth element; Described polymer solution is polyvinyl alcohol or gelatin solution; Wherein the mass volume ratio of positive electrode matrix and polymer solution is 0.25-1.0g/mL.
The compound method of the polymer solution described in step of the present invention (1) is: be that 0.1-0.5% is dissolved in the water of 60-80 ℃ with polymer by the quality percentage composition, then be chilled to room temperature and get final product.
In step of the present invention (1), mixing time is 3-8min, and washing time is 1-5 time.
Metal oxide described in step of the present invention (2) is TiO
2, ZnO, MgO, SiO
2, Al
2O
3, SnO
2Or ZrO
2Described surfactant is Aerosol OT AOT or bromination hexadecane trimethyl ammonium CTAB; Described lithium salt solution is LiCl, Li
2SO
4, LiNO
3Or the LiAc aqueous solution.
In step of the present invention (2), metal oxide is 0.005-0.015g/mL with the mass volume ratio that contains the lithium salt solution of surfactant, and wherein the molar concentration of surfactant is 2-4 mmol/L; The molar concentration of lithium salt solution is 40-80 mmol/L.
In step of the present invention (2), mixing time is 3-8min, and the ultrasonic concussion time is 10-20min, and during high-speed stirred, the rotating speed of mixer is 10000-15000rpm, and mixing time is 5-15min.
In step of the present invention (3), the mass volume ratio of powders A and solution B is 0.4-0.6 g/mL; Mixing time is 3-8min, and washing time is 1-5 time, and dry 20-28 h, obtain powder C under 50-70 ℃.
With powder C vacuumize 8-24h, at 700-800 ℃ of calcining 2-4h, obtain metallic oxide cladded anode material of lithium ion battery in step of the present invention (4).
Compared with prior art, the present invention has the following advantages:
(1) conventional method only will be wanted coating by suction-operated and be adhered to conventional positive electrode surface, want coating and coat inhomogeneously, insecure, and the wish coating that adsorbs is not more; The present invention deals with anodal material matrix surface and metal oxide surface respectively, induces coating by the active material of surface both, and coating coats evenly, and firmly, the clad ratio of wanting the coating metal oxide is high;
(2) in the present invention, wanting coating is metal oxide, and its grain shape and size are controlled, has avoided being changed into by metal hydroxides in conventional method side reaction occuring in the oxide process and transforming the problems such as incomplete.
Description of drawings
Fig. 1 is metal oxide TiO in embodiment 1
2The positive electrode matrix LiCoO that coats
2The SEM figure of sample;
Fig. 2 is coated metal oxide TiO not in embodiment 1
2LiCoO
2The SEM figure of sample.
Embodiment
Following examples only are used for setting forth the present invention, and protection scope of the present invention is not only to be confined to following examples.The those of ordinary skill of described technical field all can be realized purpose of the present invention according to above content disclosed by the invention and scope that each parameter is got.
Embodiment 1
(1) 200mg polyvinyl alcohol (PVA) is dissolved in the 100mL water of 60 ℃, is chilled to room temperature, obtain poly-vinyl alcohol solution;
(2) with 25g positive electrode matrix LiCoO
2Matrix adds in the 50mL poly-vinyl alcohol solution, stirs 5min, filters, and rinses 3 times, obtains powders A;
(3) with 1g metal oxide TiO
2Join in the LiCl solution that 100mL contains surfactant Aerosol OT (AOT), stir 5min, sonic oscillation 15min, again with speed stirring 10 mins of high speed agitator with 15000 rpm, obtain solution B, wherein the molar concentration of surfactant Aerosol OT (AOT) is 2 mmol/L, and the molar concentration of LiCl is 40mmol/L;
(4) the positive electrode matrix LiCoO that 20g is processed through PVAC polyvinylalcohol
2Matrix (powders A) joins 40mL TiO
2In dispersion liquid (solution B), stir 5min, filter out free TiO
2, rinse 3 times, filter, dry 24 h, obtain powder C under 60 ℃;
(5) with powder C dried overnight in a vacuum, with 750 ℃ of calcining 3 h, obtain product metallic oxide cladded anode material of lithium ion battery of the present invention.
Do not adopt metal oxide TiO as shown in Figure 1, with in accompanying drawing 2
2Clad anode material matrix phase ratio, by preparation method of the present invention, metal oxide TiO
2Can be coated on more saturated, more equably positive electrode matrix LiCoO
2The surface of particle.
Embodiment 2
(1) the 400mg gelatin is dissolved in the 200mL water of 80 ℃, is chilled to room temperature, obtain gelatin solution;
(2) with 50g positive electrode matrix LiMn
2O
4Join in 100 mL gelatin solution, stir 5min, filter, rinse 3 times, obtain powders A;
(3) with 2g metal oxide Al
2O
3Join the LiAc(lithium acetate that 200mL contains surfactant softex kw (CTAB)) in solution, stir 5 min, sonic oscillation 15 min, again with speed stirring 10 mins of high speed agitator with 12000 rpm/min, obtain solution B, wherein the molar concentration of surfactant softex kw (CTAB) is 4 mmol/L, the LiAc(lithium acetate) molar concentration of solution is 80 mmol/L;
(4) with the LiMn of 40g through the gelatin solution-treated
2O
4Matrix (powders A) joins 80mLAl
2O
3In dispersion liquid (solution B), stir 5 min, filter out free Al
2O
3, rinse 3 times, filter, dry 24 h, obtain powder C under 60 ℃;
(5) with powder C dried overnight in a vacuum, with 750 ℃ of calcining 3 h, obtain product metallic oxide cladded anode material of lithium ion battery of the present invention.
Embodiment 3
(1) 400mg polyvinyl alcohol (PVA) is dissolved in the 100mL water of 70 ℃, is chilled to room temperature, obtain poly-vinyl alcohol solution;
(2) with 50g positive electrode matrix LiNiO
3Matrix adds in the 50mL poly-vinyl alcohol solution, stirs 8min, filters, and rinses 5 times, obtains powders A;
(3) 1g metal oxide ZnO is joined the LiNiO that 200mL contains surfactant Aerosol OT (AOT)
3In solution, stir 8min, sonic oscillation 10min, then with speed stirring 15 mins of high speed agitator with 10000 rpm, obtain solution B, wherein the molar concentration of surfactant Aerosol OT (AOT) is 3 mmol/L, LiNiO
3Molar concentration be 60mmol/L;
(4) the positive electrode matrix LiNiO that 25g is processed through PVAC polyvinylalcohol
3Matrix (powders A) joins in 50mL ZnO dispersion liquid (solution B), stirs 3min, filters out free ZnO, rinses 1 time, filters, and dry 28 h, obtain powder C under 50 ℃;
(5) with powder C dried overnight in a vacuum, with 800 ℃ of calcining 2 h, obtain product metallic oxide cladded anode material of lithium ion battery of the present invention.
Embodiment 4
(1) 300mg polyvinyl alcohol (PVA) is dissolved in the 100mL water of 75 ℃, is chilled to room temperature, obtain poly-vinyl alcohol solution;
(2) with 75g positive electrode matrix Li
2SO
4Matrix adds in the 100mL poly-vinyl alcohol solution, stirs 6min, filters, and rinses 3 times, obtains powders A;
(3) with 1g metal oxide ZrO
2Join the Li that 70mL contains surfactant softex kw (CTAB)
2SO
4In solution, stir 3min, sonic oscillation 20min, then with the speed stirring 15min of high speed agitator with 10000 rpm, obtain solution B, wherein the molar concentration of surfactant softex kw (CTAB) is 2.5 mmol/L, Li
2SO
4Molar concentration be 70mmol/L;
(4) with the positive electrode matrix Li of 30g through the gelatin solution-treated
2SO
4Matrix (powders A) joins 50mL ZrO
2In dispersion liquid (solution B), stir 5min, filter out free ZrO
2, rinse 5 times, filter, dry 20 h, obtain powder C under 65 ℃;
(5) with powder C dried overnight in a vacuum, with 700 ℃ of calcining 4 h, obtain product metallic oxide cladded anode material of lithium ion battery of the present invention.
Claims (7)
1. the preparation method of a metallic oxide cladded anode material of lithium ion battery, is characterized in that, contains following steps:
(1) the positive electrode matrix is placed in polymer solution, wherein the mass volume ratio of positive electrode matrix and polymer solution is 0.25-1.0g/mL, after stirring, filter and rinsing, obtains powders A; Described polymer solution is polyvinyl alcohol or gelatin solution, and the compound method of described polymer solution is: with polymer by mass percentage content 0.1-0.5% be dissolved in the water of 60-80 ℃, then be chilled to room temperature and get final product;
(2) metal oxide is placed in the lithium salt solution that contains surfactant, metal oxide is 0.005-0.015g/mL with the mass volume ratio that contains the lithium salt solution of surfactant, after stirring, sonic oscillation, high-speed stirred again, get solution B, the molar concentration of wherein said surfactant is 2-4 mmol/L, and the molar concentration of described lithium salt solution is 40-80 mmol/L;
(3) powders A that step (1) is obtained joins in the solution B of step (2) acquisition, after stirring, filtering, then through rinsing, filters and drying, obtains powder C;
(4) with powder C drying, calcining, obtain metallic oxide cladded anode material of lithium ion battery.
2. the preparation method of metallic oxide cladded anode material of lithium ion battery according to claim 1, is characterized in that, the positive electrode matrix described in step (1) is LiCoO
2, LiMn
2O
4, LiNiO
3, LiNi
xCo
1-xO
2Or LiFePO
4, wherein, LiNi
xCo
1-xO
2In 0＜x＜1.
3. the preparation method of metallic oxide cladded anode material of lithium ion battery according to claim 1, is characterized in that, in step (1), mixing time is 3-8min, and washing time is 1-5 time.
4. the preparation method of metallic oxide cladded anode material of lithium ion battery according to claim 1, is characterized in that, the metal oxide described in step (2) is TiO
2, ZnO, MgO, SiO
2, Al
2O
3, SnO
2Or ZrO
2Described surfactant is Aerosol OT AOT or bromination hexadecane trimethyl ammonium CTAB; Described lithium salt solution is LiCl, Li
2SO
4, LiNO
3Or the LiAc aqueous solution.
5. the preparation method of metallic oxide cladded anode material of lithium ion battery according to claim 1, it is characterized in that, in step (2), mixing time is 3-8min, the sonic oscillation time is 10-20min, during high-speed stirred, the rotating speed of mixer is 10000-15000rpm, and mixing time is 5-15min.
6. the preparation method of metallic oxide cladded anode material of lithium ion battery according to claim 1, is characterized in that, in step (3), the mass volume ratio of powders A and solution B is 0.4-0.6 g/mL; Mixing time is 3-8min, and washing time is 1-5 time, and dry 20-28 h, obtain powder C under 50-70 ℃.
7. the preparation method of metallic oxide cladded anode material of lithium ion battery according to claim 1, it is characterized in that, with powder C vacuumize 8-24h, at 700-800 ℃ of calcining 2-4h, obtain metallic oxide cladded anode material of lithium ion battery in step (4).
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| CN103606707B (en) * | 2013-12-03 | 2015-09-23 | 桂林理工大学 | A kind of method improving lithium ion battery chemical property |
| CN105375005B (en) * | 2015-10-22 | 2018-01-30 | 浙江美达瑞新材料科技有限公司 | Anode material for lithium-ion batteries containing nano-scale solid solution and preparation method thereof |
| CN106997945A (en) * | 2016-01-24 | 2017-08-01 | 云南民族大学 | Amorphous state Al2O3Coat LiMn2O4Preparation method |
| CN105845926A (en) * | 2016-05-23 | 2016-08-10 | 广东邦普循环科技有限公司 | Method for aluminum cladding of positive electrode material by wet method, positive electrode material, positive electrode and battery |
| CN106972169A (en) * | 2017-05-23 | 2017-07-21 | 苏州思创源博电子科技有限公司 | A kind of tungsten coats the preparation method of lithium cobaltate cathode material |
| CN109411710A (en) * | 2017-08-17 | 2019-03-01 | 江苏津谊新能源科技有限公司 | A kind of lithium ion battery material and preparation method thereof |
| CN107473265B (en) * | 2017-08-25 | 2019-04-26 | 金川集团股份有限公司 | A kind of method of powder body material cladding titanium dioxide |
| CN109546136A (en) * | 2018-12-14 | 2019-03-29 | 淮安新能源材料技术研究院 | A kind of preparation method and product of lithium phosphate cladding ternary ionic cell positive material |
| CN111162253A (en) * | 2019-12-26 | 2020-05-15 | 上海理工大学 | Preparation method of metal oxide coated long-cycle lithium nickel manganese oxide electrode material |
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| KR101501958B1 (en) * | 2003-12-23 | 2015-03-16 | 유니버시떼 드 몬트리얼 | Process for preparing electroactive insertion compounds and electrode materials obtained therefrom |
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| CN1909270A (en) * | 2006-07-28 | 2007-02-07 | 中国科学院成都有机化学有限公司 | ZnO coated surface spinel type LiMnO positive electrode material and its preparation method |
| CN101308925A (en) * | 2008-07-04 | 2008-11-19 | 深圳市贝特瑞新能源材料股份有限公司 | Composite coated positive pole material of lithium ionic cell and preparing method thereof |
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