CN103972481A - Manufacturing method for composite material - Google Patents
Manufacturing method for composite material Download PDFInfo
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- CN103972481A CN103972481A CN201310027598.9A CN201310027598A CN103972481A CN 103972481 A CN103972481 A CN 103972481A CN 201310027598 A CN201310027598 A CN 201310027598A CN 103972481 A CN103972481 A CN 103972481A
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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
- H01M4/364—Composites as mixtures
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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
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/386—Silicon or alloys based on silicon
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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
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention provides a manufacturing method for a composite material. The method comprises the following steps: (a) providing powder; (b) mixing the powder with a first solvent so as to form a mixture; (c) adding a modifier into the mixture to allow the modifier to react with the powder, thereby obtaining surface-modified powder; (d) providing graphene oxide; (e) adding a second solvent into the graphene oxide to allow the second solvent to react with the graphene oxide, thereby forming surface-modified graphene oxide; and (f) mixing the surface-modified powder with the surface-modified graphene oxide so as to form the composite material.
Description
Technical field
The present invention relates to a kind of method of manufacturing composite material, particularly a kind of method of manufacturing silicon/graphene composite material.
Background technology
The negative pole of current business-like high energy lithium ion cell is made mainly with graphite, but its theoretical capacitance only terminates in 372mAh/g.In order to break through this capacity limit, launch widely for the research of emerging negative pole, wherein especially with tin-based material (Sn:998mAh/g, SnO
2: 780mAh/g) with the tool development potentiality of both alloy systems of silica-base material (Si:4200mAh/g).But no matter tinbase or silica-based negative material, in charge and discharge process, lithium ion entry/leave is all accompanied by violent volumetric expansion contraction, thereby usually cause alloy material disintegration and significantly reduce battery cycle life, and become the obstruction of current alloy material of cathode commercialization maximum.Wherein silica-base material is for everybody does one's utmost one of lithium cell cathode material of exploitation now, and main cause is that it is at intracrustal rich content, adds that theoretical capacitance can be up to 4200mAh/g.But because its cubical expansivity during discharging and recharging is up to 300%, often cause negative pole disintegration, cracked, electrode structure easily gets loose and efflorescence, therefore capacitance approach exhaustion rapidly under charge and discharge cycles several times, has therefore limited it for commercial applications.
In order to overcome the problem that volume change is excessive caused, in the industry cycle go up the most normal occupation mode for using conductive carbon that nanometer Si particle is wrapped up.So, except can significantly reducing silicon particle volume bulking effect problem, also can improve the not good problem of silicon conductivity, for meeting most the mode of cost effect.Graphene is mono-layer graphite, it has the two-dimension plane structure of complete sp2, successfully prepared and found that in recent years Graphene has many special natures, such as excellent mechanical strength, high-specific surface area, high electron conduction and chemical stability etc., therefore it be also used in energy science and technology aspect successively.In the prior art, silicon and Graphene can be carried out to combination and prepare silicon/graphene composite material, and be applied to lithium ion battery negative, wherein Graphene can be played the part of resilient coating role and be improved the poor conductivity of Si itself in composite material, uses and increases its battery cycle charge-discharge stability.
Although it can improve and discharge and recharge stability forming after composite material, institute's experience problem is cannot be by dispersed Si particle between graphene layer at present, thereby can cause capacitance to increase and fail with discharging and recharging the number of turns.
In order to overcome silicon particle scattering problem, prior art can be added additional material or be carried out chemical modification (chemicalfunctionalization) and improve the not good problem of silicon particle dispersion, but above-mentioned these modes all can significantly increase the synthetic cost of material.Therefore, a kind of simple and low cost of research and development can be improved the mode of silicon particle dispersions, is current problem in the urgent need to address.
Summary of the invention
A first aspect of the present invention provides a kind of method of manufacturing composite material, comprises the following step: powder (a) is provided; (b) in this mixture, add the first modification agent, make to react with this powder, to obtain the powder through surfaction; (c) provide graphene oxide; (d) in this graphene oxide, add the second modification agent, make to react with this graphene oxide, to form the graphene oxide through surfaction; And (e) this powder through surfaction is mixed with this graphene oxide through surfaction, to form this composite material.
Another aspect of the present invention provides a kind of method of powder being carried out to surfaction, comprises the following step: the modification agent with electric charge is provided; And make this modification agent be distributed in the surface of powder, make the surface of this powder there is this electric charge.
Another aspect of the present invention provides a kind of method of powder being carried out to surfaction, comprises the following step: provide modification agent, wherein this modification agent tool the first free radical and electric charge; Provide powder, wherein this powder tool second free radical; And make this first free radical and this second combined with radical, so that this powder has this electric charge.
In a specific embodiment of the present invention, provide a kind of composite material, it includes: powder, and its surface is with the first electric charge being provided by the first modification agent; And graphene oxide, its surface is with the second electric charge being provided by the second modification agent; Wherein this first electric charge and this second electric charge have different electrically.This powder can be Si powder, germanium powder or tin powder.This first modification agent can be aromatic compound, and this second modification agent can be polyion liquid.In above-mentioned specific embodiment, the content (weight ratio) of this powder in composite material can be between approximately 50% to approximately between 90%.
A kind of method of manufacturing composite material is provided in another specific embodiment of the present invention, has comprised the following step: (a) provide powder; (b) in this powder, add the first modification agent, make to react with this powder, so that the powder of surface with the first electric charge being provided by this first modification agent to be provided; (c) provide graphene oxide; (d) in this graphene oxide, add the second modification agent, make to react with this graphene oxide, so that the graphene oxide of surface with the second electric charge being provided by this second modification agent to be provided; And (e) this powder through surfaction is mixed with this graphene oxide through surfaction, to form this composite material; Wherein this first electric charge and this second electric charge have different electrically, wherein step (b) adds the first solvent, this first modification agent is reacted in this first solvent with this powder, and step (e) is to add reducing agent, to make this graphene oxide of part be reduced into Graphene, to form this composite material mixing through the nanometer powder of surfaction with this.
In another specific embodiment of the present invention, the method for above-mentioned manufacture composite material, can further comprise the following step: (a1) add deoxidation compound solution, remove the oxide of the powder surface of this upgrading.
In another specific embodiment of the present invention, the method of above-mentioned manufacture composite material, can further comprise the following step: (f) heat this mixture to specified temp, to make this graphene oxide of another part be reduced into Graphene, wherein this specified temp is between approximately 500 to 700 DEG C.
Brief description of the drawings
Figure 1A is the flow chart according to first embodiment of the invention.
1B figure is the flow chart according to second embodiment of the invention.
1C figure is the flow chart according to third embodiment of the invention.
2A figure is the flow chart according to fourth embodiment of the invention.
2B figure is the flow chart according to fifth embodiment of the invention.
2C figure is the flow chart according to sixth embodiment of the invention.
The 3rd figure is the cycle charge-discharge test characteristic schematic diagram according to the embodiment of the present invention.
Embodiment
Being specifically described as of the embodiment of the present invention is as described below, but except these are described in detail, the present invention can also implement with other embodiment widely.That is, the embodiment that scope of the present invention has not been proposed limits, and the claim that should propose with the present invention is as the criterion.
The present invention adopts simple electric charge absorption method (electric charge adhesion method) to carry out upgrading, and it belongs to the method for non-covalent bonding.It is parent material that the present invention uses graphene oxide and commercialization nano silicone particle, with by macromolecule modified positively charged in graphene oxide surface, make it positively charged; Relend by chemical mode silicon particle surface is carried out to upgrading and makes it electronegative, the mode of recycling positive and negative charge absorption forms homodisperse structure.Then use high temperature thermal reduction mode that graphene oxide is reduced, to improve the not good problem of graphene oxide conductivity, finally can prepare homodisperse silicon/graphene composite material.The present invention is also applicable to various other can be needed on the material of upgrading, for example powder, nanometer powder, particle, particle, nano particle or its combination in any.
Use simple electric charge absorption method can prepare rapidly the silicon/grapheme material of Different Silicon ratio.Result comparison with prior art, utilize simple electric charge absorption method, do not need silicon particle and Graphene to do covalent bonding, silicon particle evenly can be adsorbed on to the surface of each graphene layer, and avoid Graphene again to pile up and silicon particle rendezvous problem, so as to effective its capacitance and problem that discharges and recharges stability improved.
In one embodiment of the invention, this first modification agent can be aromatic compound, this aromatic compound can be para amidocyanogen benzoic Acid (4-Aminobenoic acid), it can provide benzoic acid free radical (i.e. the first free radical), to make this benzoic acid free radical be distributed in the surface of the powder with the second free radical, this second modification agent can be polyion liquid (Poly ionicliquid, PIL), this reducing agent can be hydrazine (Hydrazine).In addition, first solvent of the following stated can be acetonitrile (Acetonitrile), and this ester class can be isoamyl nitrite (Isoamyl nitrite), and this second solvent can be deionized water.With graphene oxide can be prepared by the Hummer method of Hummer method or improvement.
The graphene oxide that Hummer method is prepared is powdered graphite is carried out to oxidation processes and obtain with the anhydrous mixture of the concentrated sulfuric acid, sodium nitrate and potassium permanganate.And Improvement type Hummer method, they are different from Hummer method, are that graphite is different from the usage ratio of sodium nitrate.
Consult 1A to the 1C figure.The flow process 100 of Figure 1A is the method for modifying of silicon particle surface, it comprises the following step: step 101: by nano silicone powder, pour 5% hydrofluoric acid (with water and ethanol with volume ratio 1:1 preparation) into, with ultrasonic oscillation 1 hour, so as to removing the silicon dioxide of silicon particle surface; Step 102: take the nano silicone powder through hydrofluoric acid treatment of 300 milligrams, para amidocyanogen benzoic Acid (4-Aminobenoic acid with 1.64 grams, i.e. the first modification agent), and by its dispersed acetonitrile (Acetonitrile to 60 milliliters, i.e. the first solvent) in solvent to form solution, use ultrasonic oscillation 10 minutes; Step 103: in to reaction bulb, continue to pass into argon gas with avoid oxygen in the presence of, this solution is stirred, and temperature is controlled in to approximately 70 DEG C; Step 104: use syringe needle that the isoamyl nitrite of 5 milliliters (Isoamyl nitrite, i.e. ester class) is injected in this solution, make itself and this solution reaction approximately 24 hours; Step 105: use air exhaust filtering mode, by this product and separated from solvent in solution, and pour a large amount of acetone into and deionized water cleans, until lower floor's solution becomes colorless, now take out and filtered out product powder is dried, it is the silicon particle after upgrading; And step 106: the silicon particle after upgrading is deposited in vacuum drying oven.
In step 102, the surface of Si powder is originally with hydrogen base, it is after reacting with para amidocyanogen benzoic Acid, this hydrogen base can depart from from the surface of Si powder, and make silicon particle surface also form the second free radical, this second free radical of this silicon particle surface, can be with para amidocyanogen benzoic Acid at the amino (NH removing on its chemical chain
2) the rear benzoic acid free radical (i.e. the first free radical) forming, with the mode combination of chemical bonding, and formation benzoic acid is distributed in the state on Si powder surface; Now originally on para amidocyanogen benzoic Acid with negative electrical charge, by make benzoic acid free radical with the silicon particle surface of institute combination with identical negative electrical charge.With macroscopic view, it is equal to and makes silicon particle surface with this negative electrical charge.
Because Si powder had previously been passed through the processing of hydrofluoric acid, and still have the residual possibility of hydrofluoric acid, it under sour effect, likely can produce cyanide after having added acetonitrile.For avoiding personnel may be subject to the harm of cyanide poisoning in operation, therefore need to increase step: inject after isoamyl nitrite (Isoamyl nitrite) abundant stirring with syringe, to remove residual hydrofluoric acid, so as to reducing the possibility of cyanide harm.Isoamyl nitrite (Isoamyl nitrite) is general normal being used as and alleviates the poisoning choice drug of cyanogen, and the object that adds this material is for the consideration in environment and handling safety.
The surface modification method that the flow process 200 of Figure 1B is graphene oxide, it comprises the following step: step 201: the Hummer method with Hummer method or improvement is prepared graphene oxide; Step 202: by the second modification agent polyion liquid (Polyionic liquid, PIL) add graphene oxide, add again reducing agent hydrazine (Hydrazine) with redox graphene, now because a part of graphene oxide can be reduced into Graphene, and the graphene oxide of another part is not reduced, so can form the mixture of the Graphene after polyion liquid upgrading and the graphene oxide after polyion liquid upgrading; And step 203: use centrifugation, polyion liquid is separated from the mixture of this Graphene after polyion liquid upgrading and the graphene oxide after polyion liquid upgrading, and with washed with de-ionized water the Graphene after polyion liquid upgrading and this mixture of graphene oxide after polyion liquid upgrading.
All in the form of sheets, polyion liquid is positively charged macromolecule to graphene oxide and Graphene itself.In the time that graphene oxide reacts with polyion liquid (step 202), the positively charged macromolecule of polyion liquid can be bonded to graphene oxide surface, to make graphene oxide surface with identical positive charge.With macroscopic view, it is equal to and makes graphene oxide surface with this positive charge.
The flow process 300 of Fig. 1 C is the preparation method of silicon and graphene composite material, it comprises the following step: step 301: the mixture of the silicon particle that upgrading is crossed and this Graphene after polyion liquid upgrading and the graphene oxide after polyion liquid upgrading carries out blending with predetermined ratio, mixture solution is diluted to 5 mg/ml by the deionized water that re-uses the second solvent, after stirring with ultrasonic oscillation 1 hour, so as to guaranteeing that Si powder evenly mixes with the mixture of this Graphene after polyion liquid upgrading graphene oxide after polyion liquid upgrading with level; Step 302: use reduced pressure concentration machine (Rotary Evaporator) that above-mentioned mixture solution is dried at approximately 75 DEG C; Step 303: the powder being dried is placed in alumina crucible, crucible is put into tubular high temperature stove afterwards, under the mixed-gas environment of hydrogen (approximately 5%) and argon gas, adopt the heating curve of unistage type or multisection type to be heated to approximately 500 DEG C with the heating rates of approximately 2 DEG C approximately per minute, maybe can be heated to approximately 600 DEG C or approximately 700 DEG C etc., and utilize high temperature remove graphene oxide surface after polyion liquid upgrading containing oxygen functional group, to reach the object of reduction; And step 304: be finally down to room temperature in naturally cooling mode, can obtain silicon/graphene powder.
In the step 301 of Fig. 1 C, the silicon particle surface of crossing due to upgrading is with negative electrical charge, and the surface of this Graphene after polyion liquid upgrading and the graphene oxide after polyion liquid upgrading is with positive charge, therefore the two can be by charge attraction, and without carrying out covalent bonding, silicon particle evenly can be adsorbed in to Graphene and/or graphene oxide surface, and then avoid Graphene and/or graphene oxide again to pile up and the existing picture such as silicon particle gathering, therefore can obtain the effect of fine dispersion, follow-up be prepared into battery after, more can effectively improve the capacitance of battery and the stability of cycle charge-discharge.
As shown in Fig. 2 A to Fig. 2 C, remove the step of the silicon dioxide on Si powder surface with hydrofluoric acid and also can postpone carry out.The flow process 400 of 2A figure is the method for modifying of silicon particle surface, and it comprises the following step: step 401: take the nano silicone powder of 300 milligrams and the para amidocyanogen benzoic Acid of 1.64 milligrams, and be dispersed in the acetonitrile of 60 milliliters, with ultrasonic oscillation 10 minutes; Step 402: in to reaction bulb, continue to pass into argon gas with avoid oxygen in the presence of this solution is stirred, temperature is controlled at approximately 70 DEG C; Step 403: use air exhaust filtering mode, by this product and separated from solvent in solution, and pour a large amount of acetone into and deionized water cleans, until lower floor's solution becomes colorless, the product powder that now takes out and filter out is dried the silicon particle being after upgrading again; And step 404: the silicon particle after upgrading is deposited in vacuum drying oven.
The surface modification method that the flow process 500 of Fig. 2 B is graphene oxide, it comprises the following step: step 501: with the Hummer method of Hummer method or improvement, prepare graphene oxide; Step 202: polyion liquid is added to graphene oxide, then add hydrazine with redox graphene, can obtain the mixture of the Graphene after polyion liquid upgrading and the graphene oxide after polyion liquid upgrading; And step 203: use centrifugation, in the mixture of the Graphene by polyion liquid after aforementioned polyion liquid upgrading and the graphene oxide after polyion liquid upgrading, separate, and with the mixture of this Graphene after polyion liquid upgrading of washed with de-ionized water and the graphene oxide after polyion liquid upgrading.
The flow process 600 of Fig. 2 C is the preparation method of silicon and graphene composite material, it comprises the following step: step 601: the mixture of the silicon particle that upgrading is crossed and above-mentioned Graphene after polyion liquid upgrading and the graphene oxide after polyion liquid upgrading, carry out blending with predetermined ratio, and use deionized water that mixture solution is diluted, after stirring with ultrasonic oscillation 1 hour, to guarantee that Si powder evenly mixes with the mixture of above-mentioned Graphene after polyion liquid upgrading and the graphene oxide after polyion liquid upgrading; Step 602: use reduced pressure concentration machine (Rotary Evaporator) that mixture solution is dried at approximately 75 DEG C; Step 603: the powder being dried is placed in to alumina crucible, afterwards crucible is put into tubular high temperature stove, under hydrogen (approximately 5%) and argon gas gaseous mixture environment, adopt the heating curve of unistage type or multisection type with the heating rates of 2 DEG C approximately per minute, be heated to approximately 500 DEG C, maybe can be heated to approximately 600 DEG C or approximately 700 DEG C etc., so as to utilize high temperature remove graphene oxide surface after polyion liquid upgrading containing oxygen functional group, reach reduction object; Step 604: be finally down to room temperature with the natural type of cooling, can obtain silicon/graphene powder; And step 605: pour silicon/graphene powder into 5% hydrofluoric acid (with water and ethanol with volume ratio 1:1 preparation), with ultrasonic oscillation 1 hour, to remove the silicon dioxide of silicon particle surface.In above-mentioned preparation method, can further increase again step 606: use syringe needle that the isoamyl nitrite of 5 milliliters (Isoamyl nitrite) is injected in this solution, with this solution reaction approximately 24 hours, remove residual hydrofluoric acid to avoid hydrofluoric acid to form cyanide.Now can increase again step 607: use air exhaust filtering mode, utilize a large amount of acetone and deionized water to clean, until lower floor's solution becomes colorless; And step 608: obtained powder is deposited in vacuum drying oven and is dried, can obtain desired silicon/graphene composite material.
As shown in Figure 3, above obtained silicon/graphene composite material is prepared into electrode by its demonstration, and be assembled into button cell and carry out the result of charge-discharge test.As shown in FIG., the ratio taking part by weight as 75:25 is mixed silicon particle rear prepared composite material with graphene oxide, its reversible specific capacitance can reach approximately 1030 Milliampere Hours/gram; When discharging and recharging for the 100th when circle, capacitance still may be maintained at approximately 760 Milliampere Hours/gram; When discharging and recharging for the 150th when circle, specific capacitance still may maintain approximately 600 Milliampere Hours/gram, decline ratio is only 42%, it can present good cycle charge discharge electrical stability.Prepared composite material in the time that the mixed proportion of silicon particle and graphene oxide is weight ratio 67:33, its in the time discharging and recharging 100 circle, specific capacitance still have an appointment 500 Milliampere Hours/gram, decline ratio is only 40%.Other are with the prepared composite material of the mixed proportion of different silicon particles and graphene oxide, and its cycle charge discharge electrical characteristics have been shown in following the 1st table.The wherein content of silicon in composite material, can utilize thermogravimeter (Thermogravimetricanalyzer, or energy dissipation analyzer (Energy Dispersive X-ray Spectrometer TGA), EDX or abbreviation EDS) carry out quantitative analysis, the data of acquisition are also listed in table 1.
Table 1
By the test result of table 1, utilize method provided by the present invention, when the content (weight ratio) of silicon particle in composite material between approximately 50% to approximately between 90%, especially between approximately 65% to approximately between 85% time, the splendid composite material of the battery cycle charge-discharge that can be improved.
Except silicon particle, germanium particle of the same clan and tin particle also can adopt similar mode to carry out surfaction, and then are prepared into desired composite material.
The present invention illustrates as above with better embodiment; only for understanding enforcement of the present invention so as to help; non-in order to limit spirit of the present invention; and skilled personnel are after comprehension spirit of the present invention; not departing from spiritual scope of the present invention; when the variation that can do a little change retouching and be equal to is replaced, its scope of patent protection when depending on claim and etc. same domain.
Claims (10)
1. a composite material, it includes:
Powder, described powder surface is with the first electric charge being provided by the first modification agent; And
Graphene oxide, described graphene oxide surface is with the second electric charge being provided by the second modification agent;
Wherein said the first electric charge and described the second electric charge have different electrically.
2. composite material according to claim 1, wherein said powder is Si powder, germanium powder or tin powder.
3. composite material according to claim 1, wherein said the first modification agent is aromatic compound, described the second modification agent is polyion liquid.
4. composite material according to claim 1, the weight ratio of wherein said powder in composite material between approximately 50% to approximately between 90%.
5. a method of manufacturing composite material described in claim 1, comprises the following step:
(a) provide powder;
(b) in described powder, add the first modification agent, make to react with described powder, so that the powder of surface with the first electric charge being provided by described the first modification agent to be provided;
(c) provide graphene oxide;
(d) in described graphene oxide, add the second modification agent, make to react with described graphene oxide, so that the graphene oxide of surface with the second electric charge being provided by described the second modification agent to be provided; And
(e) the described powder through surfaction is mixed with the described graphene oxide through surfaction, to form described composite material;
Wherein said the first electric charge and described the second electric charge have different electrically.
6. method according to claim 5, wherein step (e) is to add reducing agent, to make the described graphene oxide of part be reduced into Graphene, to form and the described described composite material mixing through the nanometer powder of surfaction.
7. method according to claim 5, further comprises the following step:
(a1) add deoxidation compound solution, remove the oxide of the powder surface of described upgrading.
8. method according to claim 5, wherein step (b) is to add the first solvent, and described the first modification agent is reacted in described the first solvent with described powder.
9. method according to claim 5, further comprises the following step:
(f) heat described mixture to specified temp, to make graphene oxide described in another part be reduced into Graphene.
10. method according to claim 9, further comprises the following step: wherein said specified temp is between approximately 500 to 700 DEG C.
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| JP2018517256A (en) * | 2015-05-27 | 2018-06-28 | ハイドロ−ケベック | Method for protecting electrode material from moisture |
| CN108232141A (en) * | 2017-12-21 | 2018-06-29 | 中国科学院化学研究所 | A kind of silicon-carbon composite cathode material of lithium ion battery of high-pressure solid and preparation method thereof |
| CN108232141B (en) * | 2017-12-21 | 2020-08-21 | 中国科学院化学研究所 | High-compaction lithium ion battery silicon-carbon composite negative electrode material and preparation method thereof |
| CN109546120A (en) * | 2018-11-20 | 2019-03-29 | 陕西煤业化工技术研究院有限责任公司 | A kind of graphene-based Si-C composite material and preparation method thereof |
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