CN109065854A - A kind of preparation method of nano-carbon coated zinc oxide composite and the preparation method of electrode - Google Patents
A kind of preparation method of nano-carbon coated zinc oxide composite and the preparation method of electrode Download PDFInfo
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- CN109065854A CN109065854A CN201810744469.4A CN201810744469A CN109065854A CN 109065854 A CN109065854 A CN 109065854A CN 201810744469 A CN201810744469 A CN 201810744469A CN 109065854 A CN109065854 A CN 109065854A
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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
- H01M4/366—Composites as layered products
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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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
- H01M4/13—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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The present invention provides a kind of preparation method of nano-carbon coated zinc oxide composite and the preparation methods of electrode, wherein, it include: a kind of preparation method of nano-carbon coated zinc oxide composite, include the following steps: the preparation of step 1) presoma nano metal organic frame bio-MOF100: the preparation of step 2 nano-carbon coated zinc oxide: the present invention also provides a kind of preparation methods of electrode, are prepared based on nano-carbon coated zinc oxide composite described above.The present invention prepares nano-carbon coated zinc oxide composites by template of nano metal organic frame, and the effective volume expansion and reunion alleviated in zinc oxide charge and discharge process improves the cyclical stability of electrode.
Description
Technical field
The invention belongs to nano-carbon coated zinc oxide composite preparation technical fields, and in particular to a kind of nano-carbon coated
The preparation method of zinc oxide composite and the preparation method of electrode.
Background technique
Global environmental pollution and energy crisis are on the rise, thus the huge environmental pollution of bring and greenhouse effects problem
Become increasingly conspicuous, mankind's energy supply system that there is an urgent need to develop new green regenerative energy sources to replace current.Wherein wrap
More environmentally-friendly electric car and hybrid vehicle are included: being developed and design, realizes the zero-emission or small discharge of CO2；It opens energetically
The renewable energy for sending out new, such as wind energy, solar energy and tide energy energy source use form.The development in these fields, requires height
The energy storage system of effect, compared to the secondary cells such as traditional lead-acid battery, nickel-cadmium cell and nickel-metal hydride battery, lithium ion battery tool
Have the advantages that open-circuit voltage height, energy density height, long service life, security performance is superior, environmental-friendly, self discharge is small, and by
It is considered the classical energy of modern material and new energy science.Using battery and supercapacitor as the electrochemical energy storage body of representative
System, in terms of electricity generation system and supply network, effectively can not only store and transmit the energy, and can play effective use
Electric energy makes up the effect of supply and demand difference.But it is swift and violent with mixed electrical automobile, electric car and other large-scale electric equipments
Development, lithium ion battery are also faced with more challenges, improve capacity, realize fast charging and discharging, reduce cost and enhancing peace
Full property etc. becomes the Main way that scientific research personnel probes into recent years.That there are energy densities is inclined for existing commercialized lithium ion battery
It is low, the problems such as high expensive, far from meeting the needs of people.Electrode material (especially cathode) is that limiting lithium ion cell holds
One of key factor of amount, so, research and development novel anode material tool has very great significance.
Zinc oxide has special physical and chemical performance, as chemical stability is high, electrochemical couple coefficient is big, radiation absorption
Range is wide and light resistance is strong etc., is good multifunctional material, can operate with multiple fields.Compared with other materials, oxidation
Zinc has many advantages, such as that theoretical specific capacity is high, at low cost, preparation is easy and chemical stability is high, and right and wrong are often with there is application prospect
One of negative electrode material.However due to zinc oxide in charge and discharge process caused by volume expansion make it as lithium ion battery
The specific capacity of negative electrode material prepares composite material with rapid decay, by design, selects suitable material and oxo transition metal
Compound progress is compound, can buffer the volume expansion during its lithiumation, be a kind of structural stability for effectively improving electrode material
And electric conductivity, thus the method for improving material circulation stability.
Metal organic framework compound (MOFs) has higher specific surface area and can as a kind of novel porous material
The pore structure of tune, hole environment so that MOFs all have in fields such as fluorescence, sensing, gas absorption separation, catalysis it is extensive potential
Using.In recent years, based on MOFs be carrier, template or predecessor preparation composite material lithium ion battery, lithium-sulfur cell,
The electrochemical energy storages such as supercapacitor field all shows the performance more excellent than conventional method.Have due to MOFs itself
The features such as porosity, adjustable structure, has shown excellent using MOFs as the carbon-clad metal oxide of template or precursor preparation
In the various features of traditional preparation methods.On the one hand rich and varied etc. with biggish specific surface area, organic ligand due to MOFs
Feature can release a large amount of gaseous state small molecule during calcination, therefore finally obtained sample has biggish specific surface
Product, or even elastic construction particle can be obtained.On the other hand, being uniformly distributed for metallic element allows oxide uniform in MOFs
Be covered by porous carbon.
Common zinc oxide is semiconductor material, at normal temperature 3.37 e V of forbidden bandwidth with higher.Its electronic conductance
Rate is low, and charge transfer resistance and Ohmic resistance are larger, causes the kinetic activity of material poor, and high rate charge-discharge performance is paid no attention to
Think.Meanwhile in charge and discharge process, the alloying reaction of the conversion reaction of zinc oxide and zinc and metallic zinc and lithium will cause material
Expect biggish bulk effect (163%) and the variation of extreme pattern, so that zinc oxide occurs dusting, falls off, loses and collector
Between connection, and can also constantly form new surface, persistently consume lithium ion, cause capacity rapid decay.During lithiumation
The Li2O invertibity of generation is poor, consumes a large amount of lithium sources, cause for the first time irreversible capacity loss it is serious；And zinc oxide is gone back
The zinc cluster obtained after original is also easy to produce reunion, seriously affects subsequent alloying process.These disadvantages are difficult to zinc oxide material
The electrode material promoted as industrialized production and commercialization.
Summary of the invention
In view of this, there is provided a kind of preparation sides of nano-carbon coated zinc oxide composite for the main object of the present invention
The preparation method of method and electrode.
The technical solution adopted by the present invention are as follows:
A kind of preparation method of nano-carbon coated zinc oxide composite, includes the following steps:
The preparation of step 1) presoma nano metal organic frame bio-MOF100:
A: weighing molar ratio is 0.5~1.5:0.8~1.2:0.6~1.8 zinc nitrate, adenine and 4,4 '-biphenyl dicarboxyls
Acid, is added the mixed solvent of organic solvent n,N-Dimethylformamide and water, and the two ratio is 2~5:1~2；
B: by mixed solution at stirring at room temperature 18~36 hours of 20~35 DEG C, white powder is obtained；
C: white powder is washed with n,N-Dimethylformamide and anhydrous methanol respectively, and obtaining nano metal after dry has
Machine frame bio-MOF100；
The preparation of step 2 nano-carbon coated zinc oxide:
The nano metal organic frame bio-MOF100 powder that step 1) obtains is calcined under an inert atmosphere, calcination temperature range
After reaching target temperature with the heating rate of 5 DEG C/min, to stop 4h under target temperature between 600~800 DEG C, after allow it
Natural cooling obtains nano-carbon coated zinc oxide composites ZnO/C.
In step, weighing molar ratio is 1~1.5:0.8~1:1~1.8 zinc nitrate, adenine and 4,4 '-connection
Benzene dicarboxylic acid, is added the mixed solvent of organic solvent n,N-Dimethylformamide and water, and the two ratio is 3:2.
In step 2, inert atmosphere is nitrogen.
The present invention also provides a kind of preparation methods of electrode, based on nano-carbon coated zinc oxide composite wood described above
Material, includes the following steps:
The nano-carbon coated zinc oxide composites ZnO/C of synthesis is taken, using Kynoar as binder, acetylene black is conductive agent,
Mixed with 6~9:0.5 of mass ratio~2:1~2, N-Methyl pyrrolidone be solvent grind it is even, then use 300mm
Scraper by its uniform blade coating on copper foil, after be dried overnight in 80 DEG C of vacuum oven；
Copper foil material is subjected to dicing, is to electrode with lithium piece, polyethylene is diaphragm material, with the hexafluorophosphoric acid of 1mol/L
Lithium is electrolyte, mixed solvent volume ratio ethylene carbonate: methyl ethyl carbonate: diethyl carbonate=0.5~1.5:0.6~1.2:
0.8~1.2 can prepare for the electrolyte of solvent based on nano-carbon coated zinc oxide composite electrode.
The present invention has the advantage that the present invention prepares nano-carbon coated zinc oxide by template of nano metal organic frame
Compound, the effective volume expansion and reunion alleviated in zinc oxide charge and discharge process, improves the cyclical stability of electrode.In electricity
Current density is still to be maintained at 650 mAh/g after 100 circle of circulation under 100mA/g, even if 100 circle of circulation at 200~300mA/g
It is still maintained at 450 mAh/g afterwards.
Detailed description of the invention
Present invention will be further explained below with reference to the attached drawings and examples.
Fig. 1 a and Fig. 1 b are the X-ray powder diffraction figure of bio-MOF100 and zinc oxide；
Fig. 2 a and Fig. 2 b are the SEM figure of bio-MOF100 presoma and prepared nano-carbon coated zinc oxide；
The electrochemistry that Fig. 3 is ZnO/C under current density is 100 mA/g and 500 mA/g recycles schematic diagram.
Specific embodiment
Below in conjunction with attached drawing and specific embodiment, the present invention will be described in detail, herein illustrative examples of the invention
And explanation is used to explain the present invention, but not as a limitation of the invention.
Embodiment 1
The present invention provides a kind of preparation methods of nano-carbon coated zinc oxide composite, include the following steps:
The preparation of step 1) presoma nano metal organic frame bio-MOF100:
A: weighing the zinc nitrate that molar ratio is 0.5:0.8:0.6, adenine and 4, and organic solvent is added in 4 '-diphenyl dicarboxylic acids
The mixed solvent of n,N-Dimethylformamide and water, the two ratio are 2:1；
B: by mixed solution at stirring at room temperature 18 hours of 20 DEG C, white powder is obtained；
C: white powder is washed with n,N-Dimethylformamide and anhydrous methanol respectively, and obtaining nano metal after dry has
Machine frame bio-MOF100；
The preparation of step 2 nano-carbon coated zinc oxide:
The nano metal organic frame bio-MOF100 powder that step 1) obtains is calcined under an inert atmosphere, calcination temperature range
After reaching target temperature with the heating rate of 5 DEG C/min, to stop 4h under target temperature between 600 DEG C, after make it naturally cold
But, nano-carbon coated zinc oxide composites ZnO/C is obtained.
The present invention also provides a kind of preparation methods of electrode, based on nano-carbon coated zinc oxide composite wood described above
Material, includes the following steps:
The nano-carbon coated zinc oxide composites ZnO/C of synthesis is taken, using Kynoar as binder, acetylene black is conductive agent,
Mixed with mass ratio 6:0.5:1, N-Methyl pyrrolidone be solvent grind it is even, then using 300mm scraper by its
Uniform blade coating on copper foil, after be dried overnight in 80 DEG C of vacuum oven；
Copper foil material is subjected to dicing, is to electrode with lithium piece, polyethylene is diaphragm material, with the hexafluorophosphoric acid of 1mol/L
Lithium is electrolyte, mixed solvent volume ratio ethylene carbonate: methyl ethyl carbonate: diethyl carbonate=0.5:0.6:0.8 is solvent
Electrolyte can prepare based on nano-carbon coated zinc oxide composite electrode.
Embodiment 2
A kind of preparation method of nano-carbon coated zinc oxide composite, includes the following steps:
The preparation of step 1) presoma nano metal organic frame bio-MOF100:
A: weighing the zinc nitrate that molar ratio is 1:1:1, adenine and 4, and organic solvent N, N- bis- is added in 4 '-diphenyl dicarboxylic acids
The mixed solvent of methylformamide and water, the two ratio are 3:2；
B: by mixed solution at stirring at room temperature 25 hours of 25 DEG C, white powder is obtained；
C: white powder is washed with n,N-Dimethylformamide and anhydrous methanol respectively, and obtaining nano metal after dry has
Machine frame bio-MOF100；
The preparation of step 2 nano-carbon coated zinc oxide:
The nano metal organic frame bio-MOF100 powder that step 1) obtains is calcined under an inert atmosphere, calcination temperature range
After reaching target temperature with the heating rate of 5 DEG C/min, to stop 4h under target temperature between 700 DEG C, after make it naturally cold
But, nano-carbon coated zinc oxide composites ZnO/C is obtained.
The present invention also provides a kind of preparation methods of electrode, based on nano-carbon coated zinc oxide composite wood described above
Material, includes the following steps:
The nano-carbon coated zinc oxide composites ZnO/C of synthesis is taken, using Kynoar as binder, acetylene black is conductive agent,
Mixed with mass ratio 8:1:1, N-Methyl pyrrolidone be solvent grind it is even, then using 300mm scraper by its
Even blade coating on copper foil, after be dried overnight in 80 DEG C of vacuum oven；
Copper foil material is subjected to dicing, is to electrode with lithium piece, polyethylene is diaphragm material, with the hexafluorophosphoric acid of 1mol/L
Lithium is electrolyte, mixed solvent volume ratio ethylene carbonate: methyl ethyl carbonate: diethyl carbonate=1:1:1 is the electrolysis of solvent
Liquid can be prepared based on nano-carbon coated zinc oxide composite electrode.
Embodiment 3
A kind of preparation method of nano-carbon coated zinc oxide composite, includes the following steps:
The preparation of step 1) presoma nano metal organic frame bio-MOF100:
A: weighing the zinc nitrate that molar ratio is 1.5:1.2:1.8, adenine and 4, and organic solvent is added in 4 '-diphenyl dicarboxylic acids
The mixed solvent of n,N-Dimethylformamide and water, the two ratio are 5:1；
B: by mixed solution at stirring at room temperature 36 hours of 35 DEG C, white powder is obtained；
C: white powder is washed with n,N-Dimethylformamide and anhydrous methanol respectively, and obtaining nano metal after dry has
Machine frame bio-MOF100；
The preparation of step 2 nano-carbon coated zinc oxide:
The nano metal organic frame bio-MOF100 powder that step 1) obtains is calcined under an inert atmosphere, calcination temperature range
After reaching target temperature with the heating rate of 5 DEG C/min, to stop 4h under target temperature between 800 DEG C, after make it naturally cold
But, nano-carbon coated zinc oxide composites ZnO/C is obtained.
The present invention also provides a kind of preparation methods of electrode, based on nano-carbon coated zinc oxide composite wood described above
Material, includes the following steps:
The nano-carbon coated zinc oxide composites ZnO/C of synthesis is taken, using Kynoar as binder, acetylene black is conductive agent,
Mixed with mass ratio 9:2:2, N-Methyl pyrrolidone be solvent grind it is even, then using 300mm scraper by its
Uniform blade coating on copper foil, after be dried overnight in 80 DEG C of vacuum oven；
Copper foil material is subjected to dicing, is to electrode with lithium piece, polyethylene is diaphragm material, with the hexafluorophosphoric acid of 1mol/L
Lithium is electrolyte, mixed solvent volume ratio ethylene carbonate: methyl ethyl carbonate: diethyl carbonate=1.5:1.2:1.2 is solvent
Electrolyte can prepare based on nano-carbon coated zinc oxide composite electrode.
Test example: the electrochemical property test of electrode.
By the electrode of above-mentioned preparation, button cell model is used to be assembled into button cell in glove box for 2032.?
Electro-chemical test, electro-chemical test major parameter setting: voltage model when cycle performance is tested are carried out in the room that temperature is 20 DEG C
0.01V-3V is enclosed, current density is 100 mA/g, 500 mA/g.
Technical solution disclosed in the embodiment of the present invention is described in detail above, specific implementation used herein
Example is expounded the principle and embodiment of the embodiment of the present invention, and the explanation of above embodiments is only applicable to help to understand
The principle of the embodiment of the present invention；At the same time, for those skilled in the art is being embodied according to an embodiment of the present invention
There will be changes in mode and application range, in conclusion the content of the present specification should not be construed as to limit of the invention
System.
Claims (4)
1. a kind of preparation method of nano-carbon coated zinc oxide composite, which comprises the steps of:
The preparation of step 1) presoma nano metal organic frame bio-MOF100:
A: weighing molar ratio is 0.5~1.5:0.8~1.2:0.6~1.8 zinc nitrate, adenine and 4,4 '-biphenyl dicarboxyls
Acid, is added the mixed solvent of organic solvent n,N-Dimethylformamide and water, and the two ratio is 2~5:1~2；
B: by mixed solution at stirring at room temperature 18~36 hours of 20~35 DEG C, white powder is obtained；
C: white powder is washed with n,N-Dimethylformamide and anhydrous methanol respectively, and obtaining nano metal after dry has
Machine frame bio-MOF100；
The preparation of step 2 nano-carbon coated zinc oxide:
The nano metal organic frame bio-MOF100 powder that step 1) obtains is calcined under an inert atmosphere, calcination temperature range
After reaching target temperature with the heating rate of 5 DEG C/min, to stop 4h under target temperature between 600~800 DEG C, after allow it
Natural cooling obtains nano-carbon coated zinc oxide composites ZnO/C.
2. the preparation method of nano-carbon coated zinc oxide composite according to claim 1, it is characterised in that: in step
In A, weighing molar ratio is 1~1.5:0.8~1:1~1.8 zinc nitrate, and adenine and 4,4 '-diphenyl dicarboxylic acids, addition has
The mixed solvent of solvent n,N-Dimethylformamide and water, the two ratio are 3:2.
3. the preparation method of nano-carbon coated zinc oxide composite according to claim 1, it is characterised in that: in step
2) in, inert atmosphere is nitrogen.
4. a kind of preparation method of electrode, based on nano-carbon coated zinc oxide composite described in claims 1 or 2 or 3,
It is characterized in that: including the following steps:
The nano-carbon coated zinc oxide composites ZnO/C of synthesis is taken, using Kynoar as binder, acetylene black is conductive agent,
Mixed with 6~9:0.5 of mass ratio~2:1~2, N-Methyl pyrrolidone be solvent grind it is even, then use 300mm
Scraper by its uniform blade coating on copper foil, after be dried overnight in 80 DEG C of vacuum oven；
Copper foil material is subjected to dicing, is to electrode with lithium piece, polyethylene is diaphragm material, with the hexafluorophosphoric acid of 1mol/L
Lithium is electrolyte, mixed solvent volume ratio ethylene carbonate: methyl ethyl carbonate: diethyl carbonate=0.5~1.5:0.6~1.2:
0.8~1.2 can prepare for the electrolyte of solvent based on nano-carbon coated zinc oxide composite electrode.
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| CN109698344A (en) * | 2019-01-16 | 2019-04-30 | 江西中汽瑞华新能源科技有限公司 | A kind of preparation method of lithium sulfur battery anode material |
| CN109962224A (en) * | 2019-03-07 | 2019-07-02 | 澳门大学 | A kind of three-dimensional carbon nanosheet-zinc oxide composites and the preparation method and application thereof |
| CN110078053A (en) * | 2019-05-16 | 2019-08-02 | 华南师范大学 | A kind of porous carbon materials and its preparation method and application applied to battery diaphragm coating |
| CN110104630A (en) * | 2019-05-16 | 2019-08-09 | 华南师范大学 | A kind of porous carbon composite and its preparation method and application for battery diaphragm |
| CN110336002A (en) * | 2019-06-26 | 2019-10-15 | 浙江大学 | Nitrogen-doped carbon-coated zinc oxide composite nano material for lithium ion battery |
| CN110853939A (en) * | 2019-10-24 | 2020-02-28 | 李建龙 | Based on biological charcoal cladding [ Zn ]4O(BDBC)3]8Super capacitor material and its making method |
| CN111584870A (en) * | 2020-05-15 | 2020-08-25 | 昆山宝创新能源科技有限公司 | Negative electrode material, preparation method thereof and battery |
| CN111697236A (en) * | 2020-04-30 | 2020-09-22 | 华南师范大学 | Three-dimensional current collector with multi-level structure for protecting lithium metal negative electrode and preparation method thereof |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109698344A (en) * | 2019-01-16 | 2019-04-30 | 江西中汽瑞华新能源科技有限公司 | A kind of preparation method of lithium sulfur battery anode material |
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| CN110078053A (en) * | 2019-05-16 | 2019-08-02 | 华南师范大学 | A kind of porous carbon materials and its preparation method and application applied to battery diaphragm coating |
| CN110104630A (en) * | 2019-05-16 | 2019-08-09 | 华南师范大学 | A kind of porous carbon composite and its preparation method and application for battery diaphragm |
| CN110336002A (en) * | 2019-06-26 | 2019-10-15 | 浙江大学 | Nitrogen-doped carbon-coated zinc oxide composite nano material for lithium ion battery |
| CN110853939A (en) * | 2019-10-24 | 2020-02-28 | 李建龙 | Based on biological charcoal cladding [ Zn ]4O(BDBC)3]8Super capacitor material and its making method |
| CN111697236A (en) * | 2020-04-30 | 2020-09-22 | 华南师范大学 | Three-dimensional current collector with multi-level structure for protecting lithium metal negative electrode and preparation method thereof |
| CN111697236B (en) * | 2020-04-30 | 2021-12-14 | 华南师范大学 | Three-dimensional current collector with multi-level structure for protecting lithium metal negative electrode and preparation method thereof |
| CN111584870A (en) * | 2020-05-15 | 2020-08-25 | 昆山宝创新能源科技有限公司 | Negative electrode material, preparation method thereof and battery |
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Application publication date: 20181221 |