CN106025180A - Lithium-ion battery cathode material GeO2/C with core-shell structure and preparation method thereof - Google Patents

Lithium-ion battery cathode material GeO2/C with core-shell structure and preparation method thereof Download PDF

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CN106025180A
CN106025180A CN201610618605.6A CN201610618605A CN106025180A CN 106025180 A CN106025180 A CN 106025180A CN 201610618605 A CN201610618605 A CN 201610618605A CN 106025180 A CN106025180 A CN 106025180A
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ion battery
geo
lithium ion
negative material
nucleocapsid structure
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张宝
孙楠
郑俊超
汤林波
杨璧源
童汇
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Central South University
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Central South University
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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
    • H01M4/362—Composites
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1393—Processes of manufacture of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • 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

Abstract

The invention provides a lithium-ion battery cathode material GeO2/C with a core-shell structure and a preparation method thereof. The GeO2/C is prepared according to the following method: (1) sufficiently dissolving germanium dioxide and a carbon source into a dispersant to obtain a mixed solution; (2) carrying out ball milling on the mixed solution obtained in the step (1) to obtain a GeO2/C precursor; and (3) sintering the GeO2/C precursor obtained in the step (2) under a protective atmosphere and cooling to a room temperature along with a furnace to obtain the lithium-ion battery cathode material GeO2/C with the core-shell structure. The GeO2/C material with the core-shell structure, which is prepared by a solid-phase method for the first time, has high specific capacity, high ion conductivity and relatively high electron conductivity, has a unique microscopic shape and has excellent electrochemical performances.

Description

Nucleocapsid structure lithium ion battery negative material GeO2/ C and preparation method thereof
Technical field
The present invention relates to a kind of lithium ion battery negative material and preparation method thereof, be specifically related to a kind of nucleocapsid structure lithium ion battery negative material GeO using solid-phase sintering technology to prepare2/ C and method thereof.
Background technology
Lithium ion battery is owing to having the plurality of advantages such as running voltage height, light weight, specific energy height, memory-less effect, pollution-free, self discharge is little, have extended cycle life so that it is become the choosing of the ideal solving energy problem.At present, along with lithium ion battery receives much concern, all achieve important application in fields such as portable electronics, mobile communication, electric automobile, Aero-Space.
The selection of ion cathode material lithium concerns the performance of lithium ion battery overall performance, traditional carbons material of commercial applications develops to high power capacity target owing to relatively low specific capacity limits lithium ion battery, therefore, find that to have height ratio capacity, high charge-discharge efficiencies, good cycle performance and security performance and low cost, free of contamination material significant.
GeO2As lithium ion battery negative material, its theoretical specific capacity is 1125 mAh/g, has higher theoretical specific capacity relative to carbons material, has higher ionic conductivity and electronic conductivity relative to silica-base material.But it is as other negative materials, in charge and discharge process, it may occur that volumetric expansion, affects performance.At present, the Volumetric expansion to most of lithium ion battery negatives, utilize cushion to alleviate its harmful effect caused more.DT Ngo et al. discloses a kind of GeO2The preparation method of/C composite, is by GeO2It is dissolved in deionized water, and adds NH4OH regulates pH=3.6, adds citric acid as carbon source, utilizes sol-gal process to obtain GeO2/ C composite.But its preparation method is follow-up also needs to high temperature pyrolysis and high-temperature calcination, and its prepared GeO2When/C composite is used as lithium ion battery negative material, owing to its particle diameter is uneven and serious agglomeration, carbon-coating can not uniformly wrap up kernel GeO2Granule, affects performance (the DT Ngo etal. Conducting of its chemical property additive-free amorphous GeO2/C composite as a high capacity and long-term stability anode for lithium ion batteries. Nanoscale, 2015,7 (6): 2552-60).
Summary of the invention
The technical problem to be solved is, overcoming the drawbacks described above that prior art exists, it is provided that a kind of height ratio capacity, high ion conductivity and electronic conductivity, bulk effect is little, preparation method is simple, the nucleocapsid structure lithium ion battery negative material GeO that synthesis temperature is low2/ C and preparation method thereof.
The technical solution adopted for the present invention to solve the technical problems is as follows: a kind of nucleocapsid structure lithium ion battery negative material GeO2/ C, makes in accordance with the following methods:
(1) germanium dioxide and carbon source are substantially soluble in dispersant, obtain mixed solution；
(2) step (1) gained mixed solution is carried out ball milling, be dried, obtain GeO2/ C presoma；
(3) by step (2) gained GeO2After/C presoma sinters under protective atmosphere, cool to room temperature with the furnace, obtain nucleocapsid structure lithium ion battery negative material GeO2/C。
Preferably, in step (1), the percent that according to carbon, described germanium dioxide is accounted for both gross masses with carbon source is 4～15%(more preferably 8～12%) ratio mix.
Preferably, in step (1), the consumption of described dispersant is so that the Solute mass fraction in mixed solution is 1～5 wt%(more preferably 2～4 wt%).
Preferably, in step (2), the rotating speed of described ball milling is 180～220rad/min(more preferably 190～210rad/min), the time of ball milling is 4～5h.On the one hand can be reduced the particle diameter of germanium dioxide by ball milling, increase its specific surface area；On the other hand, ball milling makes germanium dioxide molecule be sufficiently mixed with carbon source molecule, makes carbon source be coated on germanium dioxide molecular surface, forms nucleocapsid structure.
Preferably, in step (2), described dry temperature is 90～110 DEG C, and the time being dried is 9～11h.
Preferably, in step (3), the temperature of described sintering is 150～350 DEG C, and the time of sintering is 4～5h.
Preferably, in step (3), it is 4～5 DEG C/min from the speed of room temperature to sintering temperature.
Preferably, in step (1), described carbon source is monohydrate potassium, a glucose monohydrate, sucrose, ascorbic acid or Graphene etc..On the one hand the introducing of carbon can improve the electric conductivity of material, on the other hand, by ball milling sintering modification, makes carbon source be coated on germanium dioxide molecular surface, can form nucleocapsid structure, alleviate the Volumetric expansion of germanium dioxide, improve the chemical property of germanium dioxide.
Preferably, in step (1), described dispersant is dehydrated alcohol, ethylene glycol or Polyethylene Glycol etc..Dispersant can make germanium dioxide mix fully with carbon source, makes carbon source be evenly coated at germanium dioxide particle surface, it is simple to forms nucleocapsid structure.
Preferably, in step (3), described protective atmosphere is argon.
The know-why of the inventive method is: germanium dioxide mixes with carbon source, activates through mechanical ball milling, is controlled particle diameter, the pattern of material；The degree of crystallinity of material, the GeO of synthetic surface carbon cladding is increased by heat treatment2/ C, can remove moisture unnecessary in material by sintering simultaneously, is conducive to improving further the chemical property of germanium dioxide.To GeO2Carry out carbon cladding and form nucleocapsid structure, on the one hand can be with the electric conductivity of reinforcing material, on the other hand, owing to material with carbon element is in charge and discharge process, change in volume is little.Therefore, this nucleocapsid structure GeO2/ C composite can effectively suppress the volumetric expansion in charge and discharge process of germanium dioxide material, suppress structure collapses further, the bulk effect of material is eased and improves, make germanium class materials serve go out itself height ratio capacity, higher ionic conductivity and electronic conductivity, show the chemical property of excellence as lithium ion battery negative material.
Nucleocapsid structure GeO of the present invention2The preparation method synthesis step of/C is simple, and synthesis temperature is low, and condition is easily controllable, prepares the GeO of carbon coated core-shell structure first2/ C-material, its microstructure is that uniform class is spherical, and particle diameter is about 0.2～1.0 μm, and each spheroidal particle outer layer is coated with by carbon, and inside is germanium dioxide granule.By nucleocapsid structure GeO of the present invention2/ C-material is assembled into button cell as lithium ion battery negative material, and 0.1C first discharge specific capacity may be up to 1498.2 mAh/g, higher than GeO2The theoretical discharge specific capacity of 1125 mAh/g, and the actual discharge specific capacity of the most existing 685mAh/g.This special nucleocapsid structure anticathode material GeO2The chemical property effect of having greatly improved, show the chemical property of excellence, be a new generation's lithium ion battery negative material with higher application value.
Accompanying drawing explanation
Fig. 1 is the embodiment of the present invention 1 gained nucleocapsid structure lithium ion battery negative material GeO2The SEM figure of/C negative material；
Fig. 2 is the embodiment of the present invention 1 gained nucleocapsid structure lithium ion battery negative material GeO2The TEM figure of/C negative material；
Fig. 3 is the embodiment of the present invention 1 gained nucleocapsid structure lithium ion battery negative material GeO2/ C negative material and raw material GeO2Material discharge curve comparison diagram first under 0.1C electric current.
Detailed description of the invention
Below in conjunction with embodiment and accompanying drawing, the invention will be further described.
The density of the dehydrated alcohol that each embodiment of the following description of the present invention is used is 0.79g/mL；Other chemical reagent used, if no special instructions, is all obtained by routine business approach.
Embodiment 1
(1) 1.80g germanium dioxide and 0.2 g Graphene (wherein carbon elements 0.2g) are substantially soluble in 100 mL dehydrated alcohol, obtain mixed solution；
(2) step (1) gained mixed solution is put in ball grinder, under conditions of rotating speed 200rad/min, ball milling 4.5h, then be placed in baking oven, at 110 DEG C, it is dried 9 h, obtains GeO2/ C presoma；
(3) by step (2) gained GeO2/ C presoma is placed in pipe type sintering furnace, under an argon atmosphere, with the speed of 4 DEG C/min from room temperature to 350 DEG C, and after sintering 4h, cools to room temperature with the furnace, obtains nucleocapsid structure lithium ion battery negative material GeO2/C。
As shown in Figure 1, the present embodiment gained nucleocapsid structure lithium ion battery negative material GeO2The microscopic appearance of/C is the most spherical, and particle diameter is about 0.2～1.0 μm, and the rough material of spherical surface is exactly the result of carbon cladding, it was demonstrated that obtained the nucleocapsid structure GeO of carbon-coating cladding2/ C negative material.
As shown in Figure 2, the present embodiment gained nucleocapsid structure lithium ion battery negative material GeO2The microscopic appearance of/C is spherical GeO in dark colour core2Constitute with the core outer layer carbon shell of light colour, prove to have prepared the GeO of nucleocapsid structure further2/ C negative material.
The assembling of battery: weigh 0.24g the present embodiment gained nucleocapsid structure lithium ion battery negative material GeO2/ C, add 0.03g acetylene black (Super-P) and make conductive agent and 0.03g PVDF(HSV-900) make binding agent, 2mL NMP dispersion mixing is added after being fully ground, after sizing mixing uniformly, on the Copper Foil of 16 μ m-thick, slurry is fabricated to negative plate, with metal lithium sheet as positive pole in anaerobism glove box, with Celgard 2300 as barrier film, 1mol/L LiPF6/ EC:DMC:EMC(volume ratio 1:1:1) it is electrolyte, it is assembled into the button cell of CR2025.
From the figure 3, it may be seen that this battery is carried out charge-discharge test in 0.01～1.5V voltage range, its first discharge specific capacity under 0.1C electric current density is 1498.2 mAh/g.
Embodiment 2
(1) 1.90g germanium dioxide and 0.29 g monohydrate potassium (wherein carbon elements 0.1g) are substantially soluble in 100 mL dehydrated alcohol, obtain mixed solution；
(2) step (1) gained mixed solution is put in ball grinder, under conditions of rotating speed 180rad/min, ball milling 5h, then be placed in baking oven, at 90 DEG C, it is dried 11 h, obtains GeO2/ C presoma；
(3) by step (2) gained GeO2/ C presoma is placed in pipe type sintering furnace, under an argon atmosphere, with the speed of 4 DEG C/min from room temperature to 150 DEG C, and after sintering 5h, cools to room temperature with the furnace, obtains nucleocapsid structure lithium ion battery negative material GeO2/C。
The assembling of battery: weigh 0.24g the present embodiment gained nucleocapsid structure lithium ion battery negative material GeO2/ C, add 0.03g acetylene black (Super-P) and make conductive agent and 0.03g PVDF(HSV-900) make binding agent, 2mL NMP dispersion mixing is added after being fully ground, after sizing mixing uniformly, on the Copper Foil of 16 μ m-thick, slurry is fabricated to negative plate, with metal lithium sheet as positive pole in anaerobism glove box, with Celgard 2300 as barrier film, 1mol/L LiPF6/ EC:DMC:EMC(volume ratio 1:1:1) it is electrolyte, it is assembled into the button cell of CR2025.In 0.01～1.5V voltage range, this battery is carried out charge-discharge test, and its first discharge specific capacity under 0.1C electric current density is 1275.5 mAh/g.
Embodiment 3
(1) 1.80g germanium dioxide and 0.55g mono-glucose monohydrate (wherein carbon elements 0.2g) are substantially soluble in 100 mL dehydrated alcohol, obtain mixed solution；
(2) step (1) gained mixed solution is put in ball grinder, under conditions of rotating speed 200rad/min, ball milling 4.5h, then be placed in baking oven, at 100 DEG C, it is dried 10 h, obtains GeO2/ C presoma；
(3) by step (2) gained GeO2/ C presoma is placed in pipe type sintering furnace, under an argon atmosphere, with the speed of 4 DEG C/min from room temperature to 200 DEG C, and after sintering 4.5h, cools to room temperature with the furnace, obtains nucleocapsid structure lithium ion battery negative material GeO2/C。
The assembling of battery: weigh 0.24g the present embodiment gained nucleocapsid structure lithium ion battery negative material GeO2/ C, add 0.03g acetylene black (Super-P) and make conductive agent and 0.03g PVDF(HSV-900) make binding agent, 2mL NMP dispersion mixing is added after being fully ground, after sizing mixing uniformly, on the Copper Foil of 16 μ m-thick, slurry is fabricated to negative plate, with metal lithium sheet as positive pole in anaerobism glove box, with Celgard 2300 as barrier film, 1mol/L LiPF6/ EC:DMC:EMC(volume ratio 1:1:1) it is electrolyte, it is assembled into the button cell of CR2025.In 0.01～1.5V voltage range, this battery is carried out charge-discharge test, and its first discharge specific capacity under 0.1C electric current density is 1305.2 mAh/g.
Embodiment 4
(1) 1.70g germanium dioxide and 0.72g sucrose (wherein carbon elements 0.3g) are substantially soluble in 100 mL dehydrated alcohol, obtain mixed solution；
(2) step (1) gained mixed solution is put in ball grinder, under conditions of rotating speed 210rad/min, ball milling 4h, then be placed in baking oven, at 100 DEG C, it is dried 10h, obtains GeO2/ C presoma；
(3) by step (2) gained GeO2/ C presoma is placed in pipe type sintering furnace, under an argon atmosphere, with the speed of 5 DEG C/min from room temperature to 300 DEG C, and after sintering 4h, cools to room temperature with the furnace, obtains nucleocapsid structure lithium ion battery negative material GeO2/C。
The assembling of battery: weigh 0.24g the present embodiment gained nucleocapsid structure lithium ion battery negative material GeO2/ C, add 0.03g acetylene black (Super-P) and make conductive agent and 0.03g PVDF(HSV-900) make binding agent, 2mL NMP dispersion mixing is added after being fully ground, after sizing mixing uniformly, on the Copper Foil of 16 μ m-thick, slurry is fabricated to negative plate, with metal lithium sheet as positive pole in anaerobism glove box, with Celgard 2300 as barrier film, 1mol/L LiPF6/ EC:DMC:EMC(volume ratio 1:1:1) it is electrolyte, it is assembled into the button cell of CR2025.In 0.01～1.5V voltage range, this battery is carried out charge-discharge test, and its first discharge specific capacity under 0.1C electric current density is 1240.5 mAh/g.
Embodiment 5
(1) 1.80g germanium dioxide and 0.49g ascorbic acid (wherein carbon elements 0.2g) are substantially soluble in 100 mL dehydrated alcohol, obtain mixed solution；
(2) step (1) gained mixed solution is put in ball grinder, under conditions of rotating speed 200rad/min, ball milling 4h, then be placed in baking oven, at 105 DEG C, it is dried 9.5 h, obtains GeO2/ C presoma；
(3) by step (2) gained GeO2/ C presoma is placed in pipe type sintering furnace, under an argon atmosphere, with the speed of 4 DEG C/min from room temperature to 200 DEG C, and after sintering 4h, cools to room temperature with the furnace, obtains nucleocapsid structure lithium ion battery negative material GeO2/C。
The assembling of battery: weigh 0.24g the present embodiment gained nucleocapsid structure lithium ion battery negative material GeO2/ C, add 0.03g acetylene black (Super-P) and make conductive agent and 0.03g PVDF(HSV-900) make binding agent, 2mL NMP dispersion mixing is added after being fully ground, after sizing mixing uniformly, on the Copper Foil of 16 μ m-thick, slurry is fabricated to negative plate, with metal lithium sheet as positive pole in anaerobism glove box, with Celgard 2300 as barrier film, 1mol/L LiPF6/ EC:DMC:EMC(volume ratio 1:1:1) it is electrolyte, it is assembled into the button cell of CR2025.In 0.01～1.5V voltage range, this battery is carried out charge-discharge test, and its first discharge specific capacity under 0.1C electric current density is 1301.8 mAh/g.

Claims (10)

1. a nucleocapsid structure lithium ion battery negative material GeO2/ C, it is characterised in that make in accordance with the following methods:
(1) germanium dioxide and carbon source are substantially soluble in dispersant, obtain mixed solution；
(2) step (1) gained mixed solution is carried out ball milling, be dried, obtain GeO2/ C presoma；
(3) by step (2) gained GeO2After/C presoma sinters under protective atmosphere, cool to room temperature with the furnace, obtain nucleocapsid structure lithium ion battery negative material GeO2/C。
Nucleocapsid structure lithium ion battery negative material GeO the most according to claim 12/ C, it is characterised in that: in step (1), by described germanium dioxide and carbon source according to carbon account for the percent of both gross masses be 4～15% ratio mix.
Nucleocapsid structure lithium ion battery negative material GeO the most according to claim 1 or claim 22/ C, it is characterised in that: in step (1), the consumption of described dispersant is so that the Solute mass fraction in mixed solution is 1～5 wt%.
4. according to one of claims 1 to 3 described nucleocapsid structure lithium ion battery negative material GeO2/ C, it is characterised in that: in step (2), the rotating speed of described ball milling is 180～220rad/min, and the time of ball milling is 4～5h.
5. according to one of Claims 1 to 4 described nucleocapsid structure lithium ion battery negative material GeO2/ C, it is characterised in that: in step (2), described dry temperature is 90～110 DEG C, and the time being dried is 9～11h.
6. according to one of Claims 1 to 5 described nucleocapsid structure lithium ion battery negative material GeO2/ C, it is characterised in that: in step (3), the temperature of described sintering is 150～350 DEG C, and the time of sintering is 4～5h.
Nucleocapsid structure lithium ion battery negative material GeO the most according to claim 62/ C, it is characterised in that: in step (3), it is 4～5 DEG C/min from the speed of room temperature to sintering temperature.
8. according to one of claim 1～7 described nucleocapsid structure lithium ion battery negative material GeO2/ C, it is characterised in that: in step (1), described carbon source is monohydrate potassium, a glucose monohydrate, sucrose, ascorbic acid or Graphene.
9. according to one of claim 1～8 described nucleocapsid structure lithium ion battery negative material GeO2/ C, it is characterised in that: in step (1), described dispersant is dehydrated alcohol, ethylene glycol or Polyethylene Glycol.
10. according to one of claim 1～9 described nucleocapsid structure lithium ion battery negative material GeO2/ C, it is characterised in that: in step (3), described protective atmosphere is argon.
CN201610618605.6A 2016-08-01 2016-08-01 Lithium-ion battery cathode material GeO2/C with core-shell structure and preparation method thereof Pending CN106025180A (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107579210A (en) * 2017-07-24 2018-01-12 中南大学 A kind of lithium ion battery negative material GeOx/CNTs preparation method
CN107749472A (en) * 2017-10-20 2018-03-02 乌兰察布市大盛石墨新材料股份有限公司 A kind of high performance graphite composite negative pole material and preparation method thereof
CN108281627A (en) * 2018-01-03 2018-07-13 中国科学院上海硅酸盐研究所 A kind of lithium ion battery germanium carbon compound cathode materials and preparation method thereof
CN117712366A (en) * 2024-02-05 2024-03-15 济南中瑞泰新材料科技有限公司 Preparation method of coated electrode material, coated electrode material and lithium ion battery

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107579210A (en) * 2017-07-24 2018-01-12 中南大学 A kind of lithium ion battery negative material GeOx/CNTs preparation method
CN107579210B (en) * 2017-07-24 2020-01-14 中南大学 Preparation method of lithium ion battery negative electrode material GeOx/CNTs
CN107749472A (en) * 2017-10-20 2018-03-02 乌兰察布市大盛石墨新材料股份有限公司 A kind of high performance graphite composite negative pole material and preparation method thereof
CN107749472B (en) * 2017-10-20 2020-07-21 乌兰察布市大盛石墨新材料股份有限公司 High-performance graphite composite negative electrode material and preparation method thereof
CN108281627A (en) * 2018-01-03 2018-07-13 中国科学院上海硅酸盐研究所 A kind of lithium ion battery germanium carbon compound cathode materials and preparation method thereof
CN108281627B (en) * 2018-01-03 2021-05-25 中国科学院上海硅酸盐研究所 Germanium-carbon composite negative electrode material for lithium ion battery and preparation method thereof
CN117712366A (en) * 2024-02-05 2024-03-15 济南中瑞泰新材料科技有限公司 Preparation method of coated electrode material, coated electrode material and lithium ion battery

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