CN108134059A - A kind of negative electrode active material and preparation method for low temperature lithium battery - Google Patents

A kind of negative electrode active material and preparation method for low temperature lithium battery Download PDF

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CN108134059A
CN108134059A CN201711384342.8A CN201711384342A CN108134059A CN 108134059 A CN108134059 A CN 108134059A CN 201711384342 A CN201711384342 A CN 201711384342A CN 108134059 A CN108134059 A CN 108134059A
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oxide
low temperature
metal
active material
negative electrode
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CN108134059B (en
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陈庆
廖健淞
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Shandong Yiwei New Material Co.,Ltd.
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Chengdu New Keli Chemical Science Co Ltd
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/362Composites
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/052Li-accumulators
    • H01M10/0525Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/48Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/58Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries

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Abstract

The present invention provides a kind of negative electrode active materials and preparation method for low temperature lithium battery, selected negative material is metal and its oxide, lithium hydride, fluorination treatment is carried out to negative material surface first, negative material surface is made to form the fluorine-based reticulated porous structures of metal, surface grafting is carried out with hydroxyl organic polymer, carboxylic acid again, finally filters, obtain cathode of lithium battery active material after heat treatment.After metal and its oxide its surface fluorinated processing, form a kind of fluorine-based reticulated porous structures of metal, electrolyte is to the corrosion and passivation of negative material during reduction lithium deintercalation, simultaneously deintercalation channel is provided for lithium ion, during low temperature discharge, electrolyte decomposition occurs on the surface of this active material particle, surface forms one layer of organic solid-state dielectric film(SEI films).Lithium ion battery structure of negative electrode active material in charge and discharge process is made to be kept substantially stabilization.

Description

A kind of negative electrode active material and preparation method for low temperature lithium battery
Technical field
The present invention relates to lithium cell cathode material fields, and in particular to a kind of negative electrode active material for low temperature lithium battery And preparation method.
Background technology
The research process of lithium ion battery negative material mainly experienced for four generations.Lithium metal is first generation negative material, it Specific capacity it is higher, but due to Nature comparison it is active, Li dendrite can be generated in charge and discharge process, easily puncture diaphragm and Lead to the safety issues such as short circuit, electric leakage.The aluminium lithium alloy that the second generation uses can effectively avoid the problem that Li dendrite, still Charge and discharge cycles several times after, material, which will appear serious volume change, leads to battery material powdered, and battery structure is caused to destroy, Cycle life is low.And there is the negative material of improved oxide type, but such material is still defective. After 1980, under the guiding of Armand theories, people gradually have found, during insertion of the lithium in carbon material, electrode potential is non- Very close to the current potential in lithium metal in itself, and it is not easy to react with organic electrolyte used so that cycle performance becomes It is good.It is generally used here it is current people and commercialized third generation negative material.The reversible capacity of graphite negative electrodes material is 300~360 mAh/g.But with the demand of Battery Market, the newcooperative medical system that specific capacity is high, cycle performance is excellent and safety is good Material cause the concern of numerous researchers and make great progress, here it is forth generation negative materials, i.e. silicon, tinbase With oxide-based negative material.
Lithium ion battery has higher operating voltage and energy density, and has extended cycle life and environmental-friendly etc. excellent Gesture is widely used in production and living.With the development of modern society, the requirement to electrical appliance is also higher and higher.Compact electric apparatus Such as mobile phone, camera battery, gradually develop toward light, thin, long standby, high safety direction, and electric tool, electric bicycle, electricity Electrical automobile then requires higher energy density and safety with battery.The performance of electrode material directly determines lithium ion battery Energy density and safety, therefore it is most important to develop high-performance negative material.Carbon material is current commercial negative material, It is conductive good, stable structure, advantage cheap and easy to get, but specific capacity is than relatively low, and easily generates Li dendrite, causes to pacify Full property is poor.Metal Substrate negative material and transition metal oxide are with theoretical specific capacity is high, intercalation potential ratio is relatively low, raw material resources The series of advantages such as abundant, safety and environmental protection, but these materials generate serious expansion in de-/process of intercalation, are easy to cause The powdered of material eventually leads to the destruction of battery structure.By building metal (metal oxide) compound system, by metal or Person's transition metal oxide is dispersed on carbon material (graphite, carbon nanotube) parent.It will using carbon material (graphite, carbon nanotube) The serious metal of bulk effect and its oxide support get up, and to alleviate volume expansion, improve the chemical property of negative material, Improve stability.
In the prior art, negative electrode active material is generally using graphite, graphite have that specific capacity is high, charging and discharging curve is flat and The advantages that cheap is a kind of ideal lithium ion battery negative material, but there are first charge-discharge efficiency is low, cycle performance The shortcomings of poor, to electrolyte high selectivity, and under low-temperature condition, the discharge effect of graphite is undesirable.
Number of patent application CN2012103090617 discloses a kind of carbon negative electrode material of lithium ion cell, using graphite as core, Pyrolytic carbon is cladding raw material, and the doped carbon nanometer pipe during cladding, the lithium battery discharge performance prepared through this method is good, but The shortcomings of cryogenic property is poor, and complex process, and product cost is high, and preparation process is difficult to control.
Invention content
For existing lithium ion battery negative material low temperature discharge effect it is unstable the defects of, the present invention provides a kind of for low The preparation method of the negative electrode active material of warm lithium battery.The present invention is achieved by the following technical solutions.
A kind of preparation method of negative electrode active material for low temperature lithium battery, preparation process include the following steps:
(1)By metal and its oxide, lithium hydride in mass ratio(2~8):(1~4):(0.1~3)It is mixed;
(2)Under atmosphere of inert gases, mixed-powder is subjected to ball milling, obtains metal and its oxide/lithium hydride composite material;
(3)By metal and its oxide/lithium hydride composite material and fluorochemical in mass ratio 100:(0.5~5)It carries out equal Even mixing is ground after mixing;
(4)At a temperature of 200~800 DEG C, by step(3)The material of grinding carries out heat treatment 1~5 hour, and obtaining surface has The composite material of metal-fluorine-based reticulated porous structures;
(5)By step(4)Obtain composite material of the surface with metal-fluorine-based reticulated porous structures and hydroxy kind organic polymer Object, carboxylic acid are in mass ratio(1~5):1:1 is put into autoclave, and polar solvent is added in reaction kettle, is vigorously stirred, is molten Solution is heated to 100~200 DEG C, reacts 1~60 hour, obtains metal and its oxide/lithium hydride coordination polymer presoma, Product is washed, drying for standby;
(6)Metal and its oxide/lithium hydride coordination polymer presoma are put into the tube furnace with inert gas, are heated to It 200~800 DEG C, reacts 1~10 hour, obtains for the negative electrode active material of low temperature lithium battery.
In said program, the rotational speed of ball-mill is 300~500r/min, and Ball-milling Time is 1~30 hour, pressure 1 ~10MPa, temperature are 60~80 DEG C, and the grain size of metal and its oxide powder is 1~100 μm after ball milling.
In said program, the metal and its oxide are magnesium and its oxide, cobalt and its oxide, aluminium and its oxidation Object, germanium and its oxide, tin and its oxide, lead and its oxide, antimony and its oxide, gallium and its oxide, cadmium and its oxygen One kind in compound, silver and its oxide, manganese and its oxide, molybdenum and its oxide, vanadium and its oxide.
In said program, the fluorochemical is NH4F、NH4PF6、(NH43AlF6、NH4BF4In one kind or several Kind.
In said program, the hydroxy kind organic polymer is polyvinyl alcohol, in polyethylene glycol, end hydroxy butadiene One kind.
In said program, the carboxylic acid is polyacrylic acid, one kind in aromatic acid.
In said program, the inert gas is argon gas.
In said program, the polar solvent is water, methanol, ethyl alcohol, n,N-Dimethylformamide, N, N- dimethyl second One or more of amide.
A kind of negative electrode active material for low temperature lithium battery being prepared by the above method.
Beneficial effects of the present invention:The metal and its oxide mass specific capacity of transformant transition are higher, generally 600~ 1400mAh/g, the Li formed after embedding lithium2O has reversible electro-chemical activity, after surface fluorinated processing, forms a kind of gold Belong to-fluorine-based reticulated porous structures, reduce the corrosion and passivation of electrolyte during lithium deintercalation to negative material, while carry for lithium ion For deintercalation channel, then surface grafting hydroxyl, carboxyl, obtain metal and its oxide coordination organic polymer precursor body, into one Step reduces common insertion of the organic solvent during lithium deintercalation, and reduces the interface impedance between cathode/electrolyte, is put in low temperature In electric process, electrolyte decomposition occurs on the surface of this active material particle, surface forms one layer of organic solid-state dielectric film (SEI films).The structure for making lithium ion battery negative electrode active material in charge and discharge process is substantially stable, avoid lithium from Sub- battery in charge and discharge cycles structure back and forth stretch caused by structure destroy, further improve the low of negative electrode active material Warm cycle performance increases its service life, cycle performance more better than carbons negative material is made it have, usually in recurring number thousand After secondary, stable capacity can be still kept.
Specific embodiment
In the following, the present invention will be further described in detail by way of specific embodiments, but this should not be interpreted as to the present invention Range be only limitted to following example.Without departing from the idea of the above method of the present invention, according to ordinary skill The various replacements or change that knowledge and customary means are made, should be included in the scope of the present invention.
Embodiment 1
Step 1:By Co, CoO, LiH in mass ratio 5:2:After 2 mixing, under protection of argon gas, it is placed in ball mill and grinds, ball milling Machine rotating speed be 400r/min, ball milling 12 hours;Pressure is 3MPa;Temperature is 80 DEG C;Metal powder is crossed to 80 μm of sieve after ball milling, Unsanctioned continuation ball milling is until passing through.
Step 2:Co/CoO/LiH composite materials and NH4BF4In mass ratio 100:It is ground 1 hour after 1 mixing, then with 5 DEG C/min is heated to 800 DEG C, constant temperature 3 hours, obtaining surface has the composite material of metal-fluorine-based reticulated porous structures.
Step 3:By composite material made from step 2 and polyvinyl alcohol, polyacrylic acid in mass ratio 4:1:1 to be put into high pressure anti- It answers in kettle, adds in enough water and ethyl alcohol, high-speed stirred is heated to 160 DEG C, reacts 24 hours, obtains Co/CoO/LiH coordinations Polyacrylic acid presoma, is then washed with deionized, and is put into 80 DEG C of baking ovens dry.
Step 4:Co/CoO/LiH coordination polyacrylic acid presomas are put into tube furnace, are passed through argon gas, are heated to 600 DEG C, Reaction 4 hours, obtains for the negative electrode active material of low temperature lithium battery.
Rate charge-discharge performance is shown in Table 1, and low temperature charge-discharge performance is shown in Table 2.
1 rate charge-discharge performance of table
2 low temperature charge-discharge performance of table
Embodiment 2
Step 1:By Ni, NiO, LiH in mass ratio 5:2:After 2 mixing, under protection of argon gas, it is placed in ball mill and grinds, ball milling Machine rotating speed be 400r/min, ball milling 10 hours;Pressure is 3MPa;Temperature is 80 DEG C;Metal powder is crossed to 80 μm of sieve after ball milling, Unsanctioned continuation ball milling is until passing through.
Step 2:Ni/NiO/LiH composite materials and NH4F in mass ratio 100:Grind 1 hour after 2 mixing, then with 5 DEG C/ Min is heated to 800 DEG C, and constant temperature 3 hours, obtaining surface has the composite material of metal-fluorine-based reticulated porous structures.
Step 3:By composite material made from step 2 and polyvinyl alcohol, aromatic acid in mass ratio 4:1:1 is put into reaction under high pressure In kettle, enough n,N-Dimethylformamide and ethyl alcohol are added in, high-speed stirred is heated to 160 DEG C, reacts 24 hours, obtains Ni/ NiO/LiH is coordinated polyvinyl alcohol presoma, is then washed with deionized, and is put into 80 DEG C of baking ovens dry.
Step 4:Ni/NiO/LiH coordination polyvinyl alcohol presomas are put into tube furnace, are passed through argon gas, are heated to 600 DEG C, Reaction 4 hours, obtains for the negative electrode active material of low temperature lithium battery.
Rate charge-discharge performance is shown in Table 3, and low temperature charge-discharge performance is shown in Table 4.
3 rate charge-discharge performance of table
4 low temperature charge-discharge performance of table
Embodiment 3
Step 1:By Cu, CuO, LiH in mass ratio 5:3:After 2 mixing, under protection of argon gas, it is placed in ball mill and grinds, ball milling Machine rotating speed be 400r/min, ball milling 10 hours;Pressure is 3MPa;Temperature is 80 DEG C;Metal powder is crossed to 80 μm of sieve after ball milling, Unsanctioned continuation ball milling is until passing through.
Step 2:Cu/CuO/LiH composite materials and NH4PF6In mass ratio 100:It is ground 1 hour after 0.5 mixing, then with 5 DEG C/min is heated to 800 DEG C, constant temperature 3 hours, obtaining surface has the composite material of metal-fluorine-based reticulated porous structures.
Step 3:By composite material made from step 2 and polyvinyl alcohol, polyacrylic acid in mass ratio 4:1:1 to be put into high pressure anti- It answers in kettle, adds in enough n,N-Dimethylformamide and methanol, high-speed stirred is heated to 160 DEG C, reacts 24 hours, obtains Cu/CuO/LiH is coordinated polyvinyl alcohol presoma, is then washed with deionized, and is put into 80 DEG C of baking ovens dry.
Step 4:Cu/CuO/LiH coordination polyvinyl alcohol presomas are put into tube furnace, are passed through argon gas, are heated to 600 DEG C, Reaction 4 hours, obtains for the negative electrode active material of low temperature lithium battery.
Rate charge-discharge performance is shown in Table 5, and low temperature charge-discharge performance is shown in Table 6.
5 rate charge-discharge performance of table
6 low temperature charge-discharge performance of table
Embodiment 4
Step 1:By Mn, MnO2, LiH in mass ratio 5:3:After 2 mixing, under protection of argon gas, it is placed in ball mill and grinds, ball milling Machine rotating speed be 400r/min, ball milling 10 hours;Pressure is 3MPa;Temperature is 80 DEG C;Metal powder is crossed to 80 μm of sieve after ball milling, Unsanctioned continuation ball milling is until passing through.
Step 2:Mn/MnO2/ LiH composite materials and NH4PF6In mass ratio 100:Grind 1 hour after 0.5 mixing, then with 5 DEG C/min is heated to 800 DEG C, and constant temperature 3 hours, obtaining surface has the composite material of metal-fluorine-based reticulated porous structures.
Step 3:By composite material made from step 2 and polyethylene glycol, polyacrylic acid in mass ratio 4:1:1 to be put into high pressure anti- It answers in kettle, adds in enough n,N-dimethylacetamide and ethyl alcohol, high-speed stirred is heated to 160 DEG C, reacts 24 hours, obtains Mn/MnO2/ LiH is coordinated polyvinyl alcohol presoma, is then washed with deionized, and is put into 80 DEG C of baking ovens dry.
Step 4:Mn/MnO2/ LiH coordination polyvinyl alcohol presomas are put into tube furnace, are passed through argon gas, are heated to 600 DEG C, Reaction 4 hours, obtains for the negative electrode active material of low temperature lithium battery.
Rate charge-discharge performance is shown in Table 7, and low temperature charge-discharge performance is shown in Table 8.
7 rate charge-discharge performance of table
8 low temperature charge-discharge performance of table
Comparative example
Step 1:50 parts of petroleum cokes, 20 parts of needle cokes, 20 parts of carbonaceous mesophase spherules, 30 parts of isotropic cokes are added to ball mill It crushes, obtains mixed-powder.
Step 2:Mixed-powder and excessive perchloric acid are subjected to ultrasonic agitation 2h, then isolate powder with centrifuge, point Powder is not washed with pure water and ethyl alcohol, until pH value is 8~9, is then dried powder for 24 hours, as inert gas at 60 DEG C It protects, keep the temperature 2h at 800 DEG C, be finally cooled to room temperature, obtain expanded graphite.
Step 3:By 10 parts of expanded graphite parts by weight and 1 part of coal tar weight fraction, 50 parts of tetrahydrofuran weight fraction Mixing, high-speed stirred 1h.
Step 4:The agglomeration granulation object for being coated with carbon source is placed in inert protective atmosphere and carries out charing sintering in 1500 DEG C Handle 10h.
Step 5:Powder after charing sintering processes is placed in inert protective atmosphere, graphitization sintering is carried out at 3000 DEG C Handle 48h.
Step 6:100 parts of powder weight number after graphitization sintering processes is mixed with 10 parts of agraphitic carbon parts by weight It closes, high-speed stirred 1h obtains low temperature lithium cell cathode material.
Negative material and battery made of identical anode, diaphragm, electrolyte prepared by embodiment 1 and comparative example, into Row capacity, charge-discharge performance contrast test, test result such as table 9.Test condition:25 ± 2 DEG C, relative humidity 50~75%.
Specific capacity and the charge-discharge performance comparison for the first time of table 9
As can be seen from Table 9, there is higher ratio as the lithium ion battery of negative electrode active material using metal and its oxide Capacity, circulation volume conservation rate and better cryogenic property.

Claims (9)

1. the preparation method of a kind of negative electrode active material for low temperature lithium battery, which is characterized in that preparation process includes following Step:
(1)By metal and its oxide, lithium hydride in mass ratio(2~8):(1~4):(0.1~3)It is mixed;
(2)Under atmosphere of inert gases, mixed-powder is subjected to ball milling, obtains metal and its oxide/lithium hydride composite material;
(3)By metal and its oxide/lithium hydride composite material and fluorochemical in mass ratio 100:(0.5~5)It carries out equal Even mixing is ground after mixing;
(4)At a temperature of 200~800 DEG C, by step(3)The material of grinding carries out heat treatment 1~5 hour, and obtaining surface has The composite material of metal-fluorine-based reticulated porous structures;
(5)By step(4)Obtain composite material of the surface with metal-fluorine-based reticulated porous structures and hydroxy kind organic polymer Object, carboxylic acid are in mass ratio(1~5):1:1 is put into autoclave, and polar solvent is added in reaction kettle, is vigorously stirred, is molten Solution is heated to 100~200 DEG C, reacts 1~60 hour, obtains metal and its oxide/lithium hydride coordination polymer presoma, Product is washed, drying for standby;
(6)Metal and its oxide/lithium hydride coordination polymer presoma are put into the tube furnace with inert gas, are heated to It 200~800 DEG C, reacts 1~10 hour, obtains for the negative electrode active material of low temperature lithium battery.
2. a kind of preparation method of negative electrode active material for low temperature lithium battery according to claim 1, feature exist It is 300~500r/min in, the rotational speed of ball-mill, Ball-milling Time is 1~30 hour, and pressure is 1~10MPa, temperature 60 ~80 DEG C, the grain size of metal and its oxide powder is 1~100 μm after ball milling.
3. a kind of preparation method of negative electrode active material for low temperature lithium battery according to claim 1, feature exist In, the metal and its oxide be magnesium and its oxide, cobalt and its oxide, aluminium and its oxide, germanium and its oxide, Tin and its oxide, lead and its oxide, antimony and its oxide, gallium and its oxide, cadmium and its oxide, silver and its oxidation One kind in object, manganese and its oxide, molybdenum and its oxide, vanadium and its oxide.
4. a kind of preparation method of negative electrode active material for low temperature lithium battery according to claim 1, feature exist In the fluorochemical is NH4F、NH4PF6、(NH43AlF6、NH4BF4One or more of.
5. a kind of preparation method of negative electrode active material for low temperature lithium battery according to claim 1, feature exist In the hydroxy kind organic polymer is polyvinyl alcohol, one kind in polyethylene glycol, end hydroxy butadiene.
6. a kind of preparation method of negative electrode active material for low temperature lithium battery according to claim 1, feature exist In the carboxylic acid is polyacrylic acid, one kind in aromatic acid.
7. a kind of preparation method of negative electrode active material for low temperature lithium battery according to claim 1, feature exist In the inert gas is argon gas.
8. a kind of preparation method of negative electrode active material for low temperature lithium battery according to claim 1, feature exist In the polar solvent is water, methanol, ethyl alcohol, n,N-Dimethylformamide, one kind in n,N-dimethylacetamide or several Kind.
9. the negative electrode active material for low temperature lithium battery that any one of claim 1-8 the methods are prepared.
CN201711384342.8A 2017-12-20 2017-12-20 Negative active material for low-temperature lithium battery and preparation method thereof Active CN108134059B (en)

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CN109193026A (en) * 2018-10-17 2019-01-11 浙江工业大学 Preparation method of chalcogenide solid electrolyte
CN109256544A (en) * 2018-09-03 2019-01-22 河南克莱威纳米碳材料有限公司 A kind of lithium silion cell electrode material and preparation method thereof and a kind of lithium silion cell

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CN104045116A (en) * 2014-06-12 2014-09-17 江苏大学 Preparation method of nano porous metal oxide/carbon lithium ion battery cathode material
CN105591112A (en) * 2015-12-22 2016-05-18 北京化工大学常州先进材料研究院 Lithium air battery air electrode and preparation method

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US20130108539A1 (en) * 2011-10-28 2013-05-02 Microvast New Materials (Huzhou) Co., LTD. Method for Preparing Negative Electrode Material of Lithium Ion Battery
CN102738464A (en) * 2012-06-28 2012-10-17 浙江大学 Preparation method of lithium based compound
CN104045116A (en) * 2014-06-12 2014-09-17 江苏大学 Preparation method of nano porous metal oxide/carbon lithium ion battery cathode material
CN105591112A (en) * 2015-12-22 2016-05-18 北京化工大学常州先进材料研究院 Lithium air battery air electrode and preparation method

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109256544A (en) * 2018-09-03 2019-01-22 河南克莱威纳米碳材料有限公司 A kind of lithium silion cell electrode material and preparation method thereof and a kind of lithium silion cell
CN109256544B (en) * 2018-09-03 2020-01-14 河南克莱威纳米碳材料有限公司 Lithium-silicon battery electrode material and preparation method thereof, and lithium-silicon battery
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