CN106558686A - Preparation method of carbon-coated silicon/silicon carbide composite active material - Google Patents
Preparation method of carbon-coated silicon/silicon carbide composite active material Download PDFInfo
- Publication number
- CN106558686A CN106558686A CN201510690535.0A CN201510690535A CN106558686A CN 106558686 A CN106558686 A CN 106558686A CN 201510690535 A CN201510690535 A CN 201510690535A CN 106558686 A CN106558686 A CN 106558686A
- Authority
- CN
- China
- Prior art keywords
- silicon
- active material
- silicon carbide
- carbon coating
- carbide composite
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000010703 silicon Substances 0.000 title claims abstract description 145
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 139
- 229910010271 silicon carbide Inorganic materials 0.000 title claims abstract description 122
- 239000011149 active material Substances 0.000 title claims abstract description 112
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 title claims abstract description 109
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 101
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 85
- 239000002131 composite material Substances 0.000 title claims abstract description 71
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 239000011248 coating agent Substances 0.000 claims abstract description 85
- 238000000576 coating method Methods 0.000 claims abstract description 85
- 239000000463 material Substances 0.000 claims abstract description 75
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 43
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000010426 asphalt Substances 0.000 claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 19
- 238000010438 heat treatment Methods 0.000 claims abstract description 14
- 239000000203 mixture Substances 0.000 claims description 23
- 239000003960 organic solvent Substances 0.000 claims description 19
- 239000000853 adhesive Substances 0.000 claims description 16
- 150000001768 cations Chemical class 0.000 claims description 13
- 239000003792 electrolyte Substances 0.000 claims description 11
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims description 10
- 239000000661 sodium alginate Substances 0.000 claims description 10
- 235000010413 sodium alginate Nutrition 0.000 claims description 10
- 229940005550 sodium alginate Drugs 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 239000010439 graphite Substances 0.000 claims description 9
- 229910002804 graphite Inorganic materials 0.000 claims description 9
- 239000007770 graphite material Substances 0.000 claims description 9
- 239000000654 additive Substances 0.000 claims description 8
- 230000000996 additive effect Effects 0.000 claims description 8
- 229940084030 carboxymethylcellulose calcium Drugs 0.000 claims description 7
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical class O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 244000025254 Cannabis sativa Species 0.000 claims description 3
- 229910021385 hard carbon Inorganic materials 0.000 claims description 3
- 238000005086 pumping Methods 0.000 claims description 3
- 229910003978 SiClx Inorganic materials 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 119
- 239000002699 waste material Substances 0.000 abstract description 11
- 239000007773 negative electrode material Substances 0.000 abstract description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 12
- 239000007788 liquid Substances 0.000 description 10
- 238000002156 mixing Methods 0.000 description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 8
- 238000012360 testing method Methods 0.000 description 6
- 239000010406 cathode material Substances 0.000 description 5
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 4
- 239000002000 Electrolyte additive Substances 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- -1 Silicon carbide compound Chemical class 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 3
- 238000005520 cutting process Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 2
- 239000003990 capacitor Substances 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 description 2
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 2
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 2
- 229940105329 carboxymethylcellulose Drugs 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- 239000007792 gaseous phase Substances 0.000 description 2
- 238000000713 high-energy ball milling Methods 0.000 description 2
- 239000011295 pitch Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 208000019901 Anxiety disease Diseases 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910000676 Si alloy Inorganic materials 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- QZOVMCPHIQVUGV-UHFFFAOYSA-N [Si].[C].[Si] Chemical compound [Si].[C].[Si] QZOVMCPHIQVUGV-UHFFFAOYSA-N 0.000 description 1
- 230000036506 anxiety Effects 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000009514 concussion Effects 0.000 description 1
- 239000002173 cutting fluid Substances 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical group FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 239000011115 styrene butadiene Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
Classifications
-
- 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
-
- 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
- H01M4/134—Electrodes based on metals, Si or alloys
-
- 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
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/386—Silicon or alloys based on silicon
-
- 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
- H01M4/58—Selection 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
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Composite Materials (AREA)
- Inorganic Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a preparation method of a carbon-coated silicon/silicon carbide composite active material, which comprises the following steps: preparing a silicon/silicon carbide material; preparing asphalt material, coating the surface of silicon/silicon carbide material with asphalt material, the coating procedure includes heating procedure; and obtaining the carbon-coated silicon/silicon carbide composite active material. The obtained carbon-coated silicon/silicon carbide composite active material can be used as a negative electrode material of a lithium battery. The present invention provides a method for separating and purifying silicon purity from waste; provides a silicon composite negative electrode material for lithium battery with high capacity density and high stability and a negative electrode material for lithium battery with low cost and high capacity.
Description
Technical field
The present invention is a kind of preparation method of silicon/silicon carbide composite active material, compound especially with regard to carbon coating silicon/silicon carbide
The preparation method of active material.
Background technology
At the beginning of lithium battery develops, it is with lithium metal as negative pole, because the high reduction potential of lithium causes this system provide first
At a relatively high capacitance (gravimetric energy density 3860mAh/g, volume energy density 2060mAh/cm3).But filling
In electric process, lithium ion can be deposited on lithium an- ode surface, generate ingotism.These dendritic lithiums are once pierced
Separation layer is worn, internal short-circuit will be caused and made battery have the anxiety of combustion explosion, and be to improve its security, SONY is developed
Second generation lithium ion battery with material with carbon element as negative pole.Until now, commercially available lithium ion battery is still more with various carbon materials
Expect for its negative material.
Although the security of material with carbon element is good, its theoretical capacity is not high, therefore many researchs are devoted to send out in recent years
Exhibition has more high-capacitance, may replace the material system of carbon-based negative electrode.
Silicon holds up to the theoretical capacity of 4200mAh/g, is be commercialized negative pole now more than ten times, but silicon at present
The reason that negative pole cannot slowly be commercialized is that, when lithium ion forms Li-Si alloy phase with silicon, density diminishes, and in turn results in
Volume can be expanded into the 300～400% of script, and this violent volumetric expansion can cause the disintegration of pole plate, in turn result in the circulation longevity
Life is deteriorated；In addition the low electric conductivity of silicon also limits its application in cathode of lithium battery.
In order to overcome the two of silicium cathode big shortcomings, there are many research teams to utilize nm silicon, nm silicon rod, silicon in recent years
Film or porous nm structure prepare the good silicon composite cathode material of high power capacity and cycle life, but either utilize
Chemical gaseous phase depositing method carries out silicon thin film, nm silicon rod or high-energy ball milling and chemical synthesis prepares nm silicon grain,
Cost is very expensive, it is impossible to contend with existing graphite cathode (～15 $/Kg).
Therefore how to reduce silicium cathode manufacturing cost and provide high capacity density high stability from battery silicon composite cathode
Material is industry problem to be solved.
The Silicon Wafer of current solar breeder, it is necessary to cut using carborundum or piano wire, during cutting, nm level
Silicon and carborundum can remain in inside cutting fluid (that is, waste liquid), if these waste materials can be through programs such as purifying, i.e.,
Can be used as the best source of lithium cell cathode material.
The content of the invention
It is therefore an object of the present invention to a kind of preparation method of carbon coating silicon/silicon carbide composite active material is provided, wherein
Silicon/silicon carbide material may be from the purifying of waste liquid when Silicon Wafer cuts, therefore can the cutting of effectively utilizes Silicon Wafer it is useless
Liquid.
It is a further object of the present invention to provide a kind of carbon coating silicon/silicon carbide composite active material preparation method of low cost.
It is yet another object of the invention to provide a kind of can live as the carbon coating silicon/silicon carbide of lithium cell cathode material is compound
The preparation method of property material.
It is yet another object of the invention to provide a kind of cycle life is good, high capacity density, the cathode of lithium battery of high stability
Carbon coating silicon/silicon carbide composite active material.
Based on above-mentioned purpose, the present invention proposes a kind of preparation method of carbon coating silicon/silicon carbide composite active material, including：
Silicon/silicon carbide material is prepared, and is silicon/silicon carbide to be added in the first organic solvent and the first ultrasonic vibrating program is carried out with shape
Into silicon/silicon carbide material；Asphalt material is provided；Coating program is carried out, asphalt material is coated in into the silicon/silicon carbide material
Surface, wherein the coating program includes:Stir asphalt material and the silicon/silicon carbide material to form the first mixture；
Heating schedule is carried out to the first mixture in an inert atmosphere to obtain carbon coating silicon/silicon carbide composite active material.
Wherein, the method for preparing silicon/silicon carbide material is further included：By silicon/silicon carbide admixed graphite material and formed
Silicon/silicon carbide material.
Wherein, silicon/silicon carbide material and graphite material weight ratio are 4：3、4：4、4：One of 5.
Wherein, heating schedule is heated 1 to 24 hours with Celsius 600 to 1200 degree.
Wherein, the method for preparing asphalt material is included：Grind asphalt material；The asphalt material for having ground is had with second
Machine solvent mixes；And the asphalt material that stirring has been ground is dissolved in the second organic solvent.
Wherein, coating program is further included before heating schedule is carried out：One second Supersonic is carried out to the first mixture
Ripple shakes program；And play the part of the first mixture and pumping filtration is carried out to the mixture while stirring.
A kind of cathode of lithium battery with carbon coating silicon/silicon carbide composite active material, includes adhesive agent, electrolyte
Additive and active material, it is characterised in that active material takes from the carbon coating silicon/silicon carbide composite reactive material of preceding method
Material.
A kind of cathode of lithium battery with carbon coating silicon/silicon carbide composite active material, includes adhesive agent, electrolyte
Additive and mixed active material, it is characterised in that mixed active material includes one first active material and one second active material,
Wherein the first active material takes from the carbon coating silicon/silicon carbide composite active material of preceding method.
Wherein the second active material includes graphite, hard carbon, lithium titanyl or said mixture.
Wherein, the weight ratio that first active material accounts for the mixed active material is 1wt%～20wt%.
Wherein, adhesive agent includes one of carboxymethylcellulose calcium, sodium alginate.
Wherein, adhesive agent is further comprising one, bivalent cation.
Wherein, bivalent cation can be Ca2+、Mn2+、Sr2+One of them.
Wherein, the additive bag of electrolyte containing vinylene carbonate, fluorinated ethylene carbonate, or both mixture.
The present invention can provide following advantages：1. silicon/silicon carbide material is retrieved from waste liquid when Silicon Wafer cuts, and reaches effective profit
With the purpose of waste liquid；2. the carbon coating silicon/silicon carbide composite active material preparation method of low cost；3. carbon coating silicon/silicon carbide
Composite active material can manufacture cathode of lithium battery；4. cathode of lithium battery cycle life is good, high capacity density, high stability it
Feature.
Description of the drawings
In order to above and other objects of the present invention, feature, advantage and embodiment can be become apparent, institute's accompanying drawings
It is described as follows：
Fig. 1 is the flow chart of the carbon coating silicon/silicon carbide composite active material preparation method of the present invention.
Fig. 2 is the flow chart for preparing asphalt material of the carbon coating silicon/silicon carbide composite active material preparation method of the present invention.
Fig. 3 is the coating program flow diagram of the carbon coating silicon/silicon carbide composite active material preparation method of the present invention.
Fig. 4 is the cycle life of the embodiment 1～4 of the carbon coating silicon/silicon carbide composite active material preparation method of the present invention
Figure.
Fig. 5 is shadow of the heating schedule of the carbon coating silicon/silicon carbide composite active material preparation method of the present invention to cycle life
Ring figure.
Fig. 6 is the addition step of the graphite material of the carbon coating silicon/silicon carbide composite active material preparation method of the present invention to following
The impact figure in ring life-span.
Fig. 7 is the adhesive agent of the cathode of lithium battery with carbon coating silicon/silicon carbide composite active material of the present invention to circulating the longevity
The impact figure of life.
Fig. 8 is the additive of the electrolyte of the cathode of lithium battery with carbon coating silicon/silicon carbide composite active material of the present invention
Impact figure to cycle life.
Fig. 9 is the bivalent cation of the cathode of lithium battery with carbon coating silicon/silicon carbide composite active material of the present invention to following
The impact figure in ring life-span.
Specific embodiment
Specific embodiment here of the present invention is disclosed, however, it is necessary to be appreciated that, the disclosed embodiment only present invention's shows
Model, and which may be implemented in other equivalent variations.Additionally, the schema drawn by this case is only illustration be used, mainly
To aid in illustrating presently preferred embodiments of the present invention.Invention which is intended to be protected is with appended claims model protection domain
It is defined.
The present invention is a kind of preparation method of carbon coating silicon/silicon carbide composite active material, including：Prepare silicon/silicon carbide
Material；There is provided drip green grass or young crops material material ﹔ carries out coating program, and wherein coating program includes:Stirring asphalt material and silicon/silicon carbide material
To form the first mixture；Under inert ambient environment carry out heating schedule to the first mixture to obtain carbon coating silicon/carbonization
Silicon composite active material.The carbon coating silicon/silicon carbide composite active material for being obtained can be used as the negative material of lithium battery.This
Invention can provide the lithium of high capacity density, the lithium battery silicon composite cathode material of high stability and developing low-cost high power capacity
Cell negative electrode material.
With regard to aforementioned technology contents, feature, effect, in following cooperation schema, with regard to the preferred embodiments of the invention
Clearly can present in detailed description.
First, Fig. 1 to Fig. 3 is referred to, is the preparation method of the carbon coating silicon-carbon-silicon carbide composite active material of the present invention
1 flow chart implemented.Step 11～step 14, step 121～123 and step 131～134 are included wherein, details are as follows for which.
Step 11：Prepare silicon/silicon carbide material, be by silicon/silicon carbide add the first organic solvent, in and carry out first
Ultrasonic vibrating program, first organic solvent, the property with dissolvable asphalt material can be acetone, benzene, first
The property organic solvent of benzene, butanone or other dissolvable asphalt materials, preferred forms are acetone solvent.And the first surpass
Sound wave concussion program is 10～30 minutes, and preferred forms are 30 minutes, and main purpose is in order to by silicon/silicon carbide material
Averagely it is scattered in the first organic solvent.Silicon/silicon carbide material therein is may be from when purified Silicon Wafer cuts
Waste liquid, thus the present invention can effectively utilizes Silicon Wafer cutting waste liquid.In a step 11, addition is can further include by silicon
The step of/carborundum admixed graphite material, then aforementioned silicon/silicon carbide and graphite are added into the first organic solvent, and carry out first
Ultrasonic vibrating.The silicon/silicon carbide material includes silicon/silicon carbide and graphite material, and graphite material is sheet electrographite；
In addition, the weight ratio of silicon/silicon carbide and graphite material is 4：3、4：4 or 4：One of 5, in the present invention,
The optimal weight implemented compares 4：3.
Step 12：Which includes step 121～123, step 121 to prepare Li green grass or young crops Cai Liao ﹔：Grind asphalt material；Step
122：By the asphalt material for having ground and the second organic solvent, mix, the wherein mixing of asphalt material and the second organic solvent
Ratio is 1g/100ml, second organic solvent, the property with dissolvable asphalt material, can be acetone, benzene, first
The organic solvent of benzene, butanone or other dissolvable asphalt materials, preferred forms are acetone solvent.Preferred forms
It is that the first organic solvent and the second organic solvent adopt identical organic solvent；And step 123：Stirring makes what is ground
Asphalt material is dissolved in the second organic solvent, whipping procedure is carried out under normal temperature, mixing speed is 100r.p.m.～2000
R.p.m., preferably mixing speed is 100r.p.m.～600r.p.m., and optimal mixing speed is 400r.p.m., until pitch
Material is dissolved completely in the stopping of the second organic solvent.
Step 13：Coating program is carried out, is the surface that asphalt material is coated in silicon/silicon carbide material, coating program
Comprising step 131～134, wherein step 131：Stirring asphalt material and silicon/silicon carbide material, to form the first mixture,
This step is asphalt material and silicon/silicon carbide material to be mixed 10～30 points in the state of stirring, optimal embodiment party
Formula is 20 minutes, and mixing speed is 100r.p.m.～2000r.p.m., and preferably mixing speed is 100r.p.m.～600r.p.m.,
Optimal mixing speed is 400r.p.m.；Step 132：The second ultrasonic vibrating program is carried out to the first mixture, wherein
During the ultrasonic vibrating time is 10～30 points, preferred forms are 20 minutes；Step 133；Stirring simultaneously first mixes
Thing, and carry out pumping filter；Step 134：Heating schedule is carried out, the first mixture that step 133 is obtained is existed
Heated under inert ambient environment, heating-up temperature is Celsius 600 to 1200 degree, and preferably heating-up temperature is arrived for 800
1000 degree, preferred forms are 1000 degree Celsius, and sustaining temperature 1～24 hour, preferably sustaining temperature are 1～10
Hour, optimal sustaining temperature 3 hours.
Step 14：Carbon coating silicon/silicon carbide composite active material is obtained, is to treat that aforementioned heating schedule terminates product and blows slowly
After being cooled to room temperature, you can obtain carbon coating silicon/silicon carbide composite active material.
And the carbon coating silicon obtained according to the preparation method 1 of the carbon coating silicon/silicon carbide composite active material of the present invention/
Silicon carbide compound active material can be used as the active material of cathode of lithium battery.And the carbon coating silicon/silicon carbide of present invention manufacture is multiple
Close active material preferably coulombic efficiency and capacitance sustainment rate can be provided due to carbon coating, comparing the material without coating,
Cycle life performance can be improved.
The present invention additionally provides a kind of cathode of lithium battery with carbon coating silicon/silicon carbide composite active material, includes glutinous
Agent, the additive and active material of electrolyte, it is characterised in that active material is taken from aforementioned carbon coating silicon/silicon carbide and is combined
The preparation method 1 of active material.
Here, the preparation method of carbon coating silicon/silicon carbide composite active material as it was previously stated, here do not add statement,
Illustrate, adhesive agent can be one of carboxymethylcellulose calcium, sodium alginate；Wherein better embodiment is with marine alga
Sour sodium is used as adhesive agent, it is possible to provide preferably cycle life performance.And it is further, during slurry add divalence sun from
Son can also contribute to lifting of the battery performance in cycle life；Bivalent cation can be Ca2+、Mn2+、Sr2+Wherein it
One.Preferred embodiment is Ca2+And Sr2+。
Further, the additive bag of electrolyte is containing vinylene carbonate, fluorinated ethylene carbonate or both mixture.
Better embodiment be using vinylene carbonate, fluorinated ethylene carbonate mixture as electrolyte additive, can
Battery preferably cycle life performance is provided.
The present invention additionally provides a kind of cathode of lithium battery with carbon coating silicon/silicon carbide composite active material, includes glutinous
Agent, the additive and mixed active material of electrolyte, it is characterised in that mixed active material includes at least first active material
Material and the second active material, wherein, the first active material takes from the preparation of aforementioned carbon coating silicon/silicon carbide composite active material
Method 1.
And the second active material includes graphite, hard carbon, lithium titanyl or said mixture.First active material and the second work
The mixed weight of property material compares 1：9 or 2：8, the weight ratio of optimal enforcement is 1：9, in other words, first is active
It is 1wt%～20wt% that material accounts for the weight ratio of mixed active material, and it is 10wt%～15wt% preferably to implement weight ratio,
Optimal weight ratio of implementing is 10wt%.
It is below embodiments of the present invention, embodiment 1～4 is different pitches coating degree (with percentages show) to circulating the longevity
The impact of life, its cycle life are shown in Fig. 4.
Table one is sequentially from top to bottom without coating sample, embodiment 1～4, and embodiment 1 is 10% carbon coating, embodiment
2 is 15% carbon coating, embodiment 3 is 20% carbon coating, embodiment 4 is 28% carbon coating.And the first of each embodiment
Secondary charging capacitor amount (1st charge (mAh/g)) and first time discharge capacity (1st discharge (mAh/g)) and coulombic efficiency
(Efficiency (%))) result is also depicted in table one.
According to one result of table it is known that the sample of carbon-free coating, the coulombic efficiency only 70% of its first lap, are draped over one's shoulders with nothing
Cover sample to compare, the coulombic efficiency of embodiment 1～4 has lifting, and minimum embodiment 4,28% coating sample, its coulomb are imitated
Rate is 79.8%；Embodiment 1 is up to, 10% coating sample, coulombic efficiency can reach 85%.
And the test result through 100 circle cycle lives is shown such as Fig. 4, the sign of embodiment 1～4 respectively Ex.1～Ex.4
Its result shows respectively that such as R1～R4 the experimental result R1～R3 of embodiment 1～3 is in the capacitance after the tests of 100 circles
(Capacity, mAh/g) has dropped down to 200 or so, and optimal experimental result is 28% for 4 carbon coating amount of embodiment, passes through
The test of 100 circles possesses more than 98% capacitance sustainment rate still 600 or so.
Table one
Fig. 5, is heating schedule, and the enforcement of step 134 affects comparison diagram, show different heating temperature to carbon coating silicon/
Impact of the silicon carbide compound active material in cycle life, using 28% carbon coating amount of previous embodiment 4, and with temperature
800 degree Celsius, 900 degree, 1000 degree of process samples, its result are shown respectively such as R5, R6, R7.With Celsius 1000
The sample that degree is processed, shows with preferably cycle life.
Fig. 6, is that the enforcement of step 11 addition flake graphite affects comparison diagram, shows the addition of different flake graphites to carbon
The impact of coating silicon/silicon carbide active material cycle life.Respectively embodiment 5～7, the silicon/silicon carbide of embodiment 5:
Electrographite compares 4 for weight:3rd, the silicon/silicon carbide of embodiment 6:Electrographite compares 4 for weight:4th, the silicon of embodiment 7/
Carborundum:Electrographite compares 4 for weight:5.The heating-up temperature of 28% carbon coating amount and heating schedule is being adopted equally for 1000
Degree, holds the temperature result of 3 hours, shows such as Fig. 6, and embodiment 5～7 is respectively labeled as Ex.5～Ex.7；Experimental result is distinguished
For R8～R10.As a result show embodiment 5：Silicon/silicon carbide：It is 4 that electrographite is weight ratio:3 cycle life is optimal.
Fig. 7, is cathode of lithium battery of the present invention with carbon coating silicon/silicon carbide composite active material, imposes variety classes
The comparison of the cycle life of adhesive agent.Respectively embodiment 8～9.Embodiment 8 is as sticking together using carboxymethylcellulose calcium
Agent, embodiment 9 are as adhesive agent using sodium alginate.
Embodiment 8 is the specific proportioning as adhesive agent using carboxymethylcellulose calcium (Carboxymethyl Cellulose)
Be 62% carbon coating silicon/silicon carbide composite active material, 25% electrographite, 5% carbon black, 4% carboxymethylcellulose calcium, 4%
Styrene-butadiene latex；Embodiment 9 is then that, with sodium alginate (Sodium Alginate), specific proportioning is 62% carbon coating silicon/carbon
SiClx composite active material, 25% electrographite, 5% carbon black, 8% sodium alginate.The use of the purpose of sodium alginate is to add
Stability of the strong carbon coating silicon/silicon carbide composite active material in charging and discharging process.Its result is shown such as Fig. 7, embodiment
The result of 8 (Ex.8) is R11, the result of embodiment 9 (Ex.9) is R12, shows the circulation using sodium alginate as adhesive agent
Life-span is showed better than with carboxymethylcellulose calcium (Carboxymethyl Cellulose).
Fig. 8, is cathode of lithium battery of the present invention with carbon coating silicon/silicon carbide composite active material, imposes variety classes
Electrolyte additive cycle life comparison.Respectively embodiment 10～11.Embodiment 10 is to add in the electrolytic solution
3vol% vinylene carbonates (VC), embodiment 11 are addition 3vol%VC and 10% fluoro ethylene in the electrolytic solution
Alkene ester (FEC).Fig. 8, it is R14 that the result of embodiment 10 (Ex.10) is R13, the result of embodiment 11 (Ex.11), when
To add the FEC of 10vol% again in electrolyte, such as under bases of the VC of 3vol% as the additive of electrolyte
Embodiment 11, its cycle life performance are better than only adding 3vol%VC, such as embodiment 10.
Fig. 9, is cathode of lithium battery of the present invention with carbon coating silicon/silicon carbide composite active material, with sodium alginate
Different bivalent cation comparing to its cycle life are added during slurry as adhesive agent.Respectively embodiment
12～15.Embodiment 12 is not added with cation, embodiment 13 for addition 10%Sr2+Cation, embodiment 14 are addition
10%Ca2+Cation, embodiment 15 are addition 10%Mg2+Cation.
Table two shows the first time charging capacitor amount (1st charge (mAh/g)) and first time discharge capacity of each embodiment
(1st discharge (mAh/g)), coulombic efficiency ((Efficiency (%))) and the 100th discharge capacity (After 100th
Discharge (mAh/g)) result.
Table two
Its cycle life shows such as Fig. 9, and embodiment 12～15 is respectively labeled as SA, Sr2+、Ca2+、Mg2+, in fact
Test result and be respectively R15, R16, R17, R18.As a result show that a small amount of bivalent cation of addition can lift battery
Cycle life, wherein again with Sr2+With Ca2+Effect after addition is more significant.
In addition, embodiment 12, it is mixed active material, wherein mixed active thing by the active material in GND to be
The first active material and the second active material are included in matter, the carbon coating silicon/silicon carbide of the first active material present invention is compound to live
Property material, the second active material is graphite, by carbon coating silicon/silicon carbide composite active material and graphite with 1:9 weight ratio
Mixing forms mixed active material, that is to say, that the carbon coating silicon/silicon carbide composite active material of the first active material accounts for mixed
The weight ratio for closing active material is 10wt%.Embodiment 12 is entered with different charge-discharge velocities with above-mentioned mixed active material
The full battery testing of row, positive pole uses NMC, and according to full cell testing results, embodiment 12 can provide battery excellent steady
Ground property, and excellent battery cycle life.
Generally, the method for the present invention need not adopt chemical gaseous phase depositing method common at present to carry out silicon thin film, nm
Silicon rod or high-energy ball milling and chemical synthesis prepare nm silicon grain and prepare silicon/silicon carbide, relative to the former high cost and
Cannot contend with existing graphite cathode, the waste liquid purifying when present invention can adopt Silicon Wafer to cut is originated as silicon/silicon carbide,
Thus can reduces cost, carbon coating silicon/silicon carbide composite active material provided by the present invention can as cathode of lithium battery in addition
Preferably cycle life and stability test are provided, battery can be extended.In addition in the present invention with carbon coating
Adhesive agent, the additive of electrolyte, bivalent cation, mixing in the cathode of lithium battery of silicon/silicon carbide composite active material is lived
Property material can all provide preferably cycle life performance.
In sum, the present invention can provide following advantages：1. silicon/silicon carbide material is retrieved from waste liquid when Silicon Wafer cuts,
Reach the purpose of effectively utilizes waste liquid；2. the carbon coating silicon/silicon carbide composite active material preparation method of low cost；3. carbon is draped over one's shoulders
Cover silicon/silicon carbide composite active material and can manufacture cathode of lithium battery；4. cathode of lithium battery cycle life is good, high capacity density,
The feature of high stability.
Although the present invention is disclosed above with aforesaid preferred embodiment, so which is not limited to the present invention, any to be familiar with institute
Category technical field technology or those skilled in the art, without departing from the spirit and scope of the present invention, when can make a little changes with moisten
Adorn, therefore the scope of patent protection of the present invention must be defined depending on the defined person of this specification scope of the appended claims.
Claims (14)
1. a kind of preparation method of carbon coating silicon/silicon carbide composite active material, it is characterised in that include：
Silicon/silicon carbide material is prepared, and is silicon/silicon carbide to be added in the first organic solvent and the first ultrasonic vibrating program is carried out with shape
Into the silicon/silicon carbide material；
There is provided Li green grass or young crops Cai Liao ﹔ and
Coating program is carried out, the asphalt material is coated in into a surface of the silicon/silicon carbide material, wherein the coating program
Including:
The asphalt material and the silicon/silicon carbide material are stirred to form the first mixture；And
Heating schedule is carried out to first mixture under inert ambient environment to obtain carbon coating silicon/silicon carbide composite reactive material
Material.
2. according to the preparation method of the carbon coating silicon/silicon carbide composite active material described in claim 1, it is characterised in that system
The method of the standby silicon/silicon carbide material is further included：By the silicon/silicon carbide admixed graphite material and formed the silicon/
In carbofrax material.
3. according to the preparation method of the carbon coating silicon/silicon carbide composite active material described in claim 2, it is characterised in that institute
It is 4 to state silicon/silicon carbide material and the graphite material weight ratio：3、4：4、4：One of 5.
4. according to the preparation method of the carbon coating silicon/silicon carbide composite active material described in claim 1, it is characterised in that institute
Stating heating schedule is heated 1 to 24 hours with Celsius 600 to 1200 degree.
5. according to the preparation method of the carbon coating silicon/silicon carbide composite active material described in claim 1, it is characterised in that system
The method of the standby asphalt material is included：
Grind the asphalt material；
The asphalt material for having ground is mixed with the second organic solvent solvent；And
Stirring makes the asphalt material for having ground be dissolved in second organic solvent.
6. according to the preparation method of the carbon coating silicon/silicon carbide composite active material described in claim 1, it is characterised in that institute
Coating program is stated before the heating schedule is carried out, is further included：
Second ultrasonic vibrating program is carried out to first mixture；And
Stir first mixture and pumping filtration is carried out to first mixture simultaneously.
7. a kind of cathode of lithium battery with carbon coating silicon/silicon carbide composite active material, include adhesive agent, and electrolyte adds
Plus agent and active material, it is characterised in that the active material is taken from as obtained by the method for claim 1 to 7 any one
Coating silicon/silicon carbide composite active material.
8., according to the cathode of lithium battery with carbon coating silicon/silicon carbide composite active material described in claim 7, its feature exists
In the adhesive agent includes one of carboxymethylcellulose calcium, sodium alginate.
9. according to the cathode of lithium battery with carbon coating silicon/silicon carbide composite active material described in claim 7, its feature
It is that the cathode of lithium battery further with carbon coating silicon/silicon carbide composite active material includes bivalent cation.
10., according to the cathode of lithium battery with carbon coating silicon/silicon carbide composite active material described in claim 9, its feature exists
In the bivalent cation is Ca2+、Mn2+、Sr2+One of them.
11. according to the described cathode of lithium battery with carbon coating silicon/silicon carbide composite active material described in claim 7, its
It is characterised by, the additive bag of the electrolyte contains vinylene carbonate, fluorinated ethylene carbonate or said mixture.
A kind of 12. cathode of lithium battery with carbon coating silicon/silicon carbide composite active material, include adhesive agent, and electrolyte adds
Plus agent and mixed active material, it is characterised in that the mixed active material includes the first active material and the second active material,
It is characterized in that first active material takes from the coating silicon/carbon as obtained by the method for claim 1 to 7 any one
SiClx composite active material.
13. exist according to the cathode of lithium battery with carbon coating silicon/silicon carbide composite active material described in claim 8, its feature
In second active material includes graphite, hard carbon, lithium titanyl or said mixture.
14. exist according to the cathode of lithium battery with carbon coating silicon/silicon carbide composite active material described in claim 8, its feature
In it is 1wt%～20wt% that first active material accounts for the weight ratio of the mixed active material.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| TW104131982A TWI636614B (en) | 2015-09-30 | 2015-09-30 | Manufacturing method for a carbon-coated silicon/silicon carbide composite active material for li-ion batteries |
| TW104131982 | 2015-09-30 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106558686A true CN106558686A (en) | 2017-04-05 |
Family
ID=58418292
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510690535.0A Pending CN106558686A (en) | 2015-09-30 | 2015-10-22 | Preparation method of carbon-coated silicon/silicon carbide composite active material |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN106558686A (en) |
| TW (1) | TWI636614B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI646051B (en) * | 2018-02-07 | 2019-01-01 | 光宇材料股份有限公司 | Nitrogen-doped carbon cerium composite material and manufacturing method thereof |
Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002255529A (en) * | 2001-03-02 | 2002-09-11 | Samsung Sdi Co Ltd | Carbonaceous material and lithium secondary battery |
| CN1744358A (en) * | 2005-09-28 | 2006-03-08 | 浙江工业大学 | A kind of additive of chargeable zinc electrode, preparation method and application thereof |
| CN1909268A (en) * | 2006-07-10 | 2007-02-07 | 深圳市贝特瑞电子材料有限公司 | Lithium ion battery negative electrode material containing PC dissolvent electrolytic solution and its preparation method |
| CN101563801A (en) * | 2005-11-21 | 2009-10-21 | 纳米系统公司 | Nanowire structures comprising carbon |
| CN101609891A (en) * | 2007-07-27 | 2009-12-23 | 三星Sdi株式会社 | Si/C compound, negative active core-shell material and comprise its lithium battery |
| US20100297502A1 (en) * | 2009-05-19 | 2010-11-25 | Nanosys, Inc. | Nanostructured Materials for Battery Applications |
| CN103094538A (en) * | 2011-11-08 | 2013-05-08 | 三星Sdi株式会社 | Negative active material, method of preparing the negative active material, negative electrode and lithium battery |
| JP2013171793A (en) * | 2012-02-22 | 2013-09-02 | Mitsubishi Chemicals Corp | Negative electrode material for nonaqueous electrolyte secondary battery, method for producing the same, negative electrode for nonaqueous electrolyte secondary battery, and nonaqueous electrolyte secondary battery |
| CN103700819A (en) * | 2013-12-30 | 2014-04-02 | 合肥国轩高科动力能源股份公司 | Preparation method of silicon composite anode material provided with gradient change coating layer on surface |
| EP2778130A1 (en) * | 2011-11-10 | 2014-09-17 | General Research Institute For Nonferrous Metals | Nano-silicon/carbon composite material and preparation method therefor |
| CN104953092A (en) * | 2015-05-12 | 2015-09-30 | 浙江天能能源科技有限公司 | Lithium ion battery negative material and preparation method thereof |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4197237B2 (en) * | 2002-03-01 | 2008-12-17 | パナソニック株式会社 | Method for producing positive electrode active material |
| CA2409524A1 (en) * | 2002-10-23 | 2004-04-23 | Hydro-Quebec | Particles consisting of graphite-based cores and covered by at least one continuous or discontinuous layer, production processes and uses for such particles |
| JP5673545B2 (en) * | 2009-09-25 | 2015-02-18 | 日本ゼオン株式会社 | Lithium ion secondary battery negative electrode and lithium ion secondary battery |
| WO2014051067A1 (en) * | 2012-09-28 | 2014-04-03 | 日本ゼオン株式会社 | Lithium ion secondary battery |
| JP6413766B2 (en) * | 2012-10-05 | 2018-10-31 | 株式会社村田製作所 | Active material, method for producing active material, electrode and secondary battery |
| KR20150098610A (en) * | 2012-12-19 | 2015-08-28 | 디아이씨 가부시끼가이샤 | Active material for negative electrodes of nonaqueous secondary batteries, and nonaqueous secondary battery |
-
2015
- 2015-09-30 TW TW104131982A patent/TWI636614B/en not_active IP Right Cessation
- 2015-10-22 CN CN201510690535.0A patent/CN106558686A/en active Pending
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002255529A (en) * | 2001-03-02 | 2002-09-11 | Samsung Sdi Co Ltd | Carbonaceous material and lithium secondary battery |
| CN1744358A (en) * | 2005-09-28 | 2006-03-08 | 浙江工业大学 | A kind of additive of chargeable zinc electrode, preparation method and application thereof |
| CN101563801A (en) * | 2005-11-21 | 2009-10-21 | 纳米系统公司 | Nanowire structures comprising carbon |
| CN1909268A (en) * | 2006-07-10 | 2007-02-07 | 深圳市贝特瑞电子材料有限公司 | Lithium ion battery negative electrode material containing PC dissolvent electrolytic solution and its preparation method |
| CN101609891A (en) * | 2007-07-27 | 2009-12-23 | 三星Sdi株式会社 | Si/C compound, negative active core-shell material and comprise its lithium battery |
| US20100297502A1 (en) * | 2009-05-19 | 2010-11-25 | Nanosys, Inc. | Nanostructured Materials for Battery Applications |
| CN103094538A (en) * | 2011-11-08 | 2013-05-08 | 三星Sdi株式会社 | Negative active material, method of preparing the negative active material, negative electrode and lithium battery |
| EP2778130A1 (en) * | 2011-11-10 | 2014-09-17 | General Research Institute For Nonferrous Metals | Nano-silicon/carbon composite material and preparation method therefor |
| JP2013171793A (en) * | 2012-02-22 | 2013-09-02 | Mitsubishi Chemicals Corp | Negative electrode material for nonaqueous electrolyte secondary battery, method for producing the same, negative electrode for nonaqueous electrolyte secondary battery, and nonaqueous electrolyte secondary battery |
| CN103700819A (en) * | 2013-12-30 | 2014-04-02 | 合肥国轩高科动力能源股份公司 | Preparation method of silicon composite anode material provided with gradient change coating layer on surface |
| CN104953092A (en) * | 2015-05-12 | 2015-09-30 | 浙江天能能源科技有限公司 | Lithium ion battery negative material and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| TW201712930A (en) | 2017-04-01 |
| TWI636614B (en) | 2018-09-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103199254B (en) | A kind of graphite negative material of lithium ion battery and preparation method thereof | |
| CN110828808B (en) | Preparation method and application of lithium-sulfur battery positive electrode material | |
| CN104641435B (en) | Carbonaceous material for negative electrodes of lithium ion capacitors and method for producing same | |
| CN107994217B (en) | Preparation method of double-coated silicon-based composite material and lithium ion battery | |
| CN105118971B (en) | A kind of lithium ion battery negative material and preparation method thereof | |
| CN108807917B (en) | Nitrogen-sulfur double-doped graphene composite silicon-boron-carbon-nitrogen ceramic composite material, preparation method and application | |
| JP6843861B2 (en) | Lithium-ion battery Negative electrode material and its manufacturing method and lithium-ion battery | |
| CN109616629A (en) | A kind of benefit lithium positive electrode active materials, positive electrode, lithium ion battery and its preparation and application | |
| CN108539172B (en) | Preparation method of composite spherical positive electrode material of high-power water-based zinc ion battery | |
| CN104641499A (en) | Carbonaceous material for negative electrodes of nonaqueous electrolyte secondary batteries and method for producing same | |
| CN102891306A (en) | Lithium ion battery Si/Li4Ti5O12/CNT composite negative pole material and preparation method thereof | |
| CN105870427B (en) | Lithium ion battery negative electrode material, preparation method thereof and lithium ion battery | |
| CN108682813A (en) | A kind of preparation method and application of Si-C composite material | |
| CN106159236A (en) | A kind of quick charge lithium titanate composite negative pole pole piece and lithium ion battery | |
| CN106992318A (en) | A kind of lithium-ion-power cell and preparation method thereof | |
| CN108682804B (en) | Preparation method of lithium ion battery cathode material with hard carbon-coated soft carbon | |
| CN109428081A (en) | Battery, positive electrode slurry, pole piece and method for removing impurity lithium | |
| CN108807896A (en) | A kind of preparation method of nitrogen-doped carbon cladding Si-C composite material | |
| CN114597341A (en) | Modified pre-lithiated silica material, preparation method and application thereof, and lithium ion battery | |
| CN115954443A (en) | Preparation method of carbon-coated silicon-copper alloy negative electrode material of lithium ion battery | |
| CN105895880A (en) | Preparation method of silicon dioxide composite material for negative electrode of lithium-ion battery | |
| WO2020155565A1 (en) | Preparation method and use method for positive electrode material of aluminum chloride-carbon battery | |
| CN106558686A (en) | Preparation method of carbon-coated silicon/silicon carbide composite active material | |
| CN105742619B (en) | A kind of unformed Mn oxide cladding ferriferous oxide lithium/anode material of lithium-ion battery and preparation method thereof | |
| CN108735995A (en) | Composite material and preparation method, cell positive material and battery |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20170405 |