CN103811721B - A kind of preparation method of lithium battery cathode plate - Google Patents
A kind of preparation method of lithium battery cathode plate Download PDFInfo
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- CN103811721B CN103811721B CN201210475295.9A CN201210475295A CN103811721B CN 103811721 B CN103811721 B CN 103811721B CN 201210475295 A CN201210475295 A CN 201210475295A CN 103811721 B CN103811721 B CN 103811721B
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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
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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
- H01M4/1393—Processes of manufacture of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
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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
- H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
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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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- 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 present invention is applied to the negative material technical field of lithium battery there is provided a kind of preparation method of lithium battery cathode plate, the described method comprises the following steps：Prepare graphene microchip；Graphene microchip is subjected to surface modification；The graphene microchip that surface is modified mixes nano silicon particles and graphene silica hybrid material is made；Graphene silicon nano power powder composite material is made in graphene silica hybrid material；And make the lithium battery cathode plate for meeting material based on graphene silicon nanopowder.Other lithium cell cathode materials are contrasted, are had the following advantages：Capacity is big, can reach 1200mAh/g；Charge/discharge rates are fast, can reach more than 5C；Have extended cycle life.
Description
Technical field
The invention belongs to the negative material technical field of lithium battery, more particularly to a kind of preparation side of lithium battery cathode plate
Method.
Background technology
Currently commercialization lithium cell cathode material be essentially all carbon negative pole material, such as electrographite, native graphite,
Carbonaceous mesophase spherules, petroleum coke, carbon fiber, thermal decomposed resins carbon etc..The negative material of also non-commercialization has：1. tin base cathode material
Material：Tin base cathode material can be divided into two kinds of the oxide and Sn-polymetallic orefield of tin.2. lithium-containing transition metal nitride negative pole
Material.3. alloy type negative material：Closed including kamash alloy, silicon-base alloy, germanium-base alloy, acieral, antimony-containing alloy, magnesium-based
Golden and other alloys.4. nanoscale negative material：CNT, Nanoalloy material.5. nanometer oxide material：It is many at present
Company is had begun to using nano-titanium oxide and nano silicon oxide addition in graphite traditional in the past, tin-oxide, CNT
The inside, greatly improves the impulse electricity amount and discharge and recharge number of times of lithium battery.
Graphene, is the Colloidal particles that carbon atom is arranged according to hexagonal.As single layer of carbon atom planar materials,
Graphene can be obtained by peeling off graphite material.This graphite crystal film of graphene is from 2004 by University of Manchester
Scientist find after, just turn into scientific circles and industrial quarters focus of attention.The thickness of graphene only has 0.335 nanometer, no
Only it is one kind most thin in known materials, also unusual rigid；As simple substance, it has transmitted the speed ratio of electronics at room temperature
Know that all conductor and semiconductor are all fast, the migration velocity of electronics has reached the 1/300 of the light velocity in graphene.Meanwhile, it is used as list
Layer atomic structure of carbon, the theoretical specific surface area of graphene is up to 2630m2/g.So high specific surface area causes with based on graphite
The material of alkene turns into extremely promising energy storage active material.
In addition, the constant current theoretical capacity of silica-base material reaches 4200mAh/g, it is significantly larger than commercial graphite cathode material
(372mAh/g), is the lithium cell cathode material of great exploitation potential.But during embedding and removing silicon materials volume
Expand, microstructure changes and causes the life-span shorter.
The content of the invention
There is provided the suitable low cost industry of one kind for the problems of the prior art that aim to overcome that of the embodiment of the present invention
Change large-scale production, preparation method that is high-quality, reducing the poisonous lithium battery cathode plate for dumping thing.
The embodiment of the present invention is achieved in that a kind of preparation method of lithium battery cathode plate, and methods described includes following
Step：Prepare graphene microchip；Graphene microchip is subjected to surface modification；The graphene microchip that surface is modified mixes silicon nanometer
Graphene-silica hybrid material is made in particle；Graphene-silicon nano power powder composite material is made in graphene-silica hybrid material；And
Make the lithium battery cathode plate for meeting material based on graphene-silicon nanopowder.
In a preferred embodiment, the preparation graphene microchip comprises the following steps：Prepare expanded graphite；By what is obtained
Expanded graphite is mixed with organic solvent；Expanded graphite organic solvent mixed liquor is subjected to ultrasound dissociation and obtains graphene microchip suspension
Liquid；And extract graphene microchip from graphene microchip suspension.
In a preferred embodiment, it is described to prepare expanded graphite expansible graphite is placed in into metal or ceramic crucible
In, under inert gas shielding, 300-900 degree is heated to, 10-60 points of keeping temperature realizes fully expansion, is then cooled to room
Temperature.
In a preferred embodiment, it is described to prepare expanded graphite expansible graphite is placed in into ceramic crucible or vierics
In ware, heated 10-60 seconds with 600-1200W microwaves, realize fully expansion, be then cooled to room temperature.
In a preferred embodiment, described be mixed into obtained expanded graphite and organic solvent puts gained expanded graphite
In container, 100-1000ml organic solvents are poured into, are stirred.
In a preferred embodiment, the organic solvent is at least one in NMP, DMP, toluene, chlorobenzene and trichloro ethylene
Kind.
In a preferred embodiment, it is described expanded graphite organic solvent mixed liquor to be subjected to ultrasound dissociation to obtain graphene micro-
Piece suspension is to be vibrated 1-24 hours under the conditions of sonic oscillation power is 300-1200W, while heating-up temperature is 20-150 degree,
Obtain graphene microchip suspension.
In a preferred embodiment, it is by stone obtained by ultrasound that graphene microchip is extracted in the suspension from graphene microchip
Black alkene microplate suspension stands 0.2-5 hours, removes upper strata suspension, removes sediment, is dried after filtering in 80 degree of baking ovens.
In a preferred embodiment, it is described by graphene microchip progress surface be modified as by gained graphene microchip add it is dense
In sulfuric acid, keep the temperature of solution to be less than 4 DEG C, be slowly added potassium permanganate, the temperature of solution is not exceeded in adding procedure
10℃；After potassium permanganate addition is finished, less than 10 DEG C magnetic agitation 90min of temperature of solution are kept；Then, in magnetic agitation
In the case of, deionized water is slowly added, while ensureing that the temperature of solution is less than 40 DEG C；Hydrogen peroxide is added, continues to stir 15min；
Last filtering drying obtains surface modified graphite alkene microplate.
In a preferred embodiment, the graphene microchip that surface is modified mix nano silicon particles obtain graphene-
Silica hybrid material is to add the surface modified graphite alkene microplate of gained in deionized water, keeps the temperature of solution to be less than 35 DEG C,
Ultrasonic disperse 10-60min；Nano silicon particles are added in deionized water, ultrasonic disperse 30-60min；Nano silicon particles are held
Easily mixed with surface modified graphite alkene solution, keep solution temperature to be less than 35 DEG C, ultrasonic disperse 30-60min；Finally, filter out
Solution, obtains surface modified graphite alkene-silica hybrid material.
In a preferred embodiment, it is described that graphene-silicon nano power powder composite material is made in graphene-silica hybrid material
For the 300-1000 DEG C of annealing 0.1-2h under inert atmosphere protection, graphene-silicon nano power powder composite material is obtained.
In a preferred embodiment, it is described to make the lithium battery cathode plate for meeting material based on graphene-silicon nanopowder
For using being coated with or rolling pressure method, lithium battery cathode plate is made in metal foil substrate.
In an embodiment of the present invention, other lithium cell cathode materials are contrasted, are had the following advantages：1. capacity is big, Ke Yida
To 1200mAh/g；2. charge/discharge rates are fast, more than 5C can be reached；3. have extended cycle life.
Embodiment
In order to make the purpose , technical scheme and advantage of the present invention be clearer, with reference to embodiments, to the present invention
It is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, and without
It is of the invention in limiting.
In an embodiment of the present invention, by carrying out surface modification to graphene microchip, then adsorb silicon nanopowder and obtain
Simultaneously the lithium battery cathode plate based on graphene-silicon nano power powder composite material is made in graphene-silicon nano power powder composite material.
Details are as follows：
First, graphene microchip is prepared；
1. prepare expanded graphite：Expansible graphite is placed in metal or ceramic crucible, under inert gas shielding, plus
Heat realizes fully expansion, is then cooled to room temperature to 300-900 degree.
Or expansible graphite is placed in ceramic crucible or glassware, 10-60 is heated with 600-1200W microwaves
Second, fully expansion is realized, room temperature is then cooled to.
In a particular embodiment, raw material also can use crystalline flake graphite.
2. obtained expanded graphite is mixed with organic solvent：Gained expanded graphite is placed in container, 100- is poured into
1000ml organic solvents, the organic solvent is NMP, DMP, toluene, chlorobenzene or trichloro ethylene, is stirred.
3. expanded graphite organic solvent mixed liquor is carried out into ultrasound dissociation obtains graphene microchip suspension：In sonic oscillation
Power is heated simultaneously to be vibrated under the conditions of 300-1200W 1-24 hours, and temperature is 20-150 degree, obtains graphene microchip suspension
Liquid.The ultrasonic disperse time is too short within 60 minutes, so that the effect of scattered dissociation is bad, the present invention is small using concussion 1-24
When, it can effectively improve dispersion effect.The heating taken in addition is also beneficial to improve dispersion effect.
4. extract graphene microchip from graphene microchip suspension：Graphene microchip suspension obtained by ultrasound is stood
0.2-5 hours, upper strata suspension is taken, sediment is removed, dried after filtering in 80 degree of baking ovens.The present invention without centrifugal treating,
Fabrication steps are saved, production efficiency is improved.
Graphene microchip is carried out surface modification by two,：
In the concentrated sulfuric acid that gained graphene microchip is added to 20-100ml, keep the temperature of solution to be less than 4 DEG C, be slowly added
0.5-20g potassium permanganate, the temperature of solution does not exceed 10 DEG C in adding procedure.After potassium permanganate addition is finished, keep
Less than 10 DEG C magnetic agitation 90min of the temperature of solution.Then, in the case of magnetic agitation, be slowly added 150ml go from
Sub- water, while ensureing that the temperature of solution is less than 40 DEG C.3ml hydrogen peroxide is added, continues to stir 15min.Last filtering drying is obtained
To surface modified graphite alkene microplate.
The graphene microchip that surface is modified by three, mixes nano silicon particles and obtains graphene-silica hybrid material：
The surface modified graphite alkene microplate of gained is added in 50-500ml deionized waters, keeps the temperature of solution to be less than 35
DEG C, ultrasonic disperse 10-60min.0.5-5g nano silicon particles (30-200nm particle diameters) are added in 500ml deionized waters, surpassed
Sound disperses 30-60min.Nano silicon particles are easily mixed with surface modified graphite alkene solution, keep solution temperature to be less than 35 DEG C,
Ultrasonic disperse 30-60min.Finally, solution is filtered out, surface modified graphite alkene-silica hybrid material is obtained.
Graphene-silicon nano power powder composite material is made in graphene-silica hybrid material by four,：Under inert atmosphere protection
300-1000 DEG C of annealing 0.1-2h, obtains graphene-silicon nano power powder composite material.
Five, are using coating or roll pressure method, and lithium battery cathode plate is made in metal foil substrate.
Presently preferred embodiments of the present invention is described in further detail below：
Embodiment one
The implementation stream of cathode of lithium battery piece preparation method based on graphene-silicon nano power powder composite material in the present embodiment
Journey is as follows：
1g50 mesh expansible graphites are placed in metal or ceramic crucible, under inert gas shielding, 900 are heated to
Degree.Gained expanded graphite is placed in container, 250ml NMP is poured into, stirs, is then 1000W in sonic oscillation power
Under the conditions of vibrate 8 hours, simultaneously heat, heating-up temperature be 80 degree.Filtering drying, obtains graphene microchip.By gained graphene
Microplate is added in the 100ml concentrated sulfuric acid, is kept the temperature of solution to be less than 4 DEG C, is slowly added 0.5g potassium permanganate, was adding
The temperature of solution does not exceed 10 DEG C in journey.Keep less than 10 DEG C magnetic agitation 90min of temperature of solution.Then, stirred in magnetic force
In the case of mixing, 150ml deionized water is slowly added, while ensureing that the temperature of solution is less than 40 DEG C.Add 3ml dioxygen
Water, continues to stir 15min.Filtering drying obtains surface modified graphite alkene microplate.The surface modified graphite alkene microplate of gained is added
Enter in 200ml deionized waters, keep the temperature of solution to be less than 35 DEG C, ultrasonic disperse 10-60min.By 0.5g nano silicon particles
(50nm particle diameters) is added in 200ml deionized waters, ultrasonic disperse 30min.By nano silicon particles solution and surface modified graphite
Alkene solution is mixed, and keeps solution temperature to be less than 35 DEG C, ultrasonic disperse 30-60min.Solution is filtered out, drying obtains surface modification
Graphene-silica hybrid material.800 DEG C of annealing 1h, obtain graphene-silicon nano power powder composite material under inert atmosphere protection.
Using being coated with or rolling pressure method, lithium battery cathode plate is made in metal foil substrate.
Embodiment two
The implementation stream of cathode of lithium battery piece preparation method based on graphene-silicon nano power powder composite material in the present embodiment
Journey is as follows：
1g expansible graphites are placed in ceramic crucible or glassware, heated 30 seconds with 800W microwaves.Then cool down
To room temperature.Gained expanded graphite is placed in container, 250ml NMP is poured into, stirs, is then in sonic oscillation power
Vibrate 8 hours, heat simultaneously under the conditions of 1000W, heating-up temperature is 80 degree.Filtering drying, obtains graphene microchip.By gained stone
Black alkene microplate is added in the 100ml concentrated sulfuric acid, is kept the temperature of solution to be less than 4 DEG C, is slowly added 0.5g potassium permanganate, is adding
Plus during the temperature of solution do not exceed 10 DEG C.Keep less than 10 DEG C magnetic agitation 90min of temperature of solution.Then, in magnetic
In the case that power is stirred, 150ml deionized water is slowly added, while ensureing that the temperature of solution is less than 40 DEG C.Add the double of 3ml
Oxygen water, continues to stir 15min.Filtering drying obtains surface modified graphite alkene microplate.By the surface modified graphite alkene microplate of gained
Add in 200ml deionized waters, keep the temperature of solution to be less than 35 DEG C, ultrasonic disperse 10-60min.By 0.5g nano silicon particles
(50nm particle diameters) is added in 200ml deionized waters, ultrasonic disperse 30min.By nano silicon particles solution and surface modified graphite
Alkene solution is mixed, and keeps solution temperature to be less than 35 DEG C, ultrasonic disperse 30-60min.Solution is filtered out, drying obtains surface modification
Graphene-silica hybrid material.800 DEG C of annealing 1h, obtain graphene-silicon nano power powder composite material under inert atmosphere protection.
Using being coated with or rolling pressure method, lithium battery cathode plate is made in metal foil substrate.
Embodiment three
The implementation stream of cathode of lithium battery piece preparation method based on graphene-silicon nano power powder composite material in the present embodiment
Journey is as follows：
1g crystalline flake graphites are placed in container, 100ml NMP is poured into, stirs, are then in sonic oscillation power
Vibrate 8 hours, heat simultaneously under the conditions of 1000W, heating-up temperature is 80 degree.Filtering drying, obtains graphene microchip.By gained stone
Black alkene microplate is added in the 50ml concentrated sulfuric acid, is kept the temperature of solution to be less than 4 DEG C, is slowly added 0.5g potassium permanganate, is adding
Plus during the temperature of solution do not exceed 10 DEG C.Keep less than 10 DEG C magnetic agitation 90min of temperature of solution.Then, in magnetic
In the case that power is stirred, 100ml deionized water is slowly added, while ensureing that the temperature of solution is less than 40 DEG C.Add the double of 3ml
Oxygen water, continues to stir 15min.Filtering drying obtains surface modified graphite alkene microplate.By the surface modified graphite alkene microplate of gained
Add in 200ml deionized waters, keep the temperature of solution to be less than 35 DEG C, ultrasonic disperse 10-60min.By 0.5g nano silicon particles
(50nm particle diameters) is added in 200ml deionized waters, ultrasonic disperse 30min.By nano silicon particles solution and surface modified graphite
Alkene solution is mixed, and keeps solution temperature to be less than 35 DEG C, ultrasonic disperse 30-60min.Solution is filtered out, drying obtains surface modification
Graphene-silica hybrid material.800 DEG C of annealing 1h, obtain graphene-silicon nano power powder composite material under inert atmosphere protection.
Using being coated with or rolling pressure method, lithium battery cathode plate is made in metal foil substrate.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all essences in the present invention
Any modifications, equivalent substitutions and improvements made within refreshing and principle etc., should be included in the scope of the protection.
Claims (9)
1. a kind of preparation method of lithium battery cathode plate, it is characterised in that the described method comprises the following steps：
Prepare graphene microchip；
Graphene microchip is subjected to surface modification；
The graphene microchip that surface is modified mixes nano silicon particles and graphene-silica hybrid material is made；
Graphene-silicon nano power powder composite material is made in graphene-silica hybrid material；And
Make the lithium battery cathode plate based on graphene-silicon nano power powder composite material；
Wherein, the preparation graphene microchip specifically includes and first prepares expanded graphite, then by obtained expanded graphite with it is organic
Solvent is mixed, then the progress ultrasound dissociation of expanded graphite organic solvent mixed liquor is obtained into graphene microchip suspension, finally from stone
Graphene microchip is extracted in black alkene microplate suspension；It is described that graphene microchip progress surface is modified as gained graphene microchip
Add in the concentrated sulfuric acid, keep the temperature of solution to be less than 4 DEG C, be slowly added potassium permanganate, the temperature of solution is not in adding procedure
Will be more than 10 DEG C；After potassium permanganate addition is finished, less than 10 DEG C magnetic agitation 90min of temperature of solution are kept；Then, in magnetic force
In the case of stirring, deionized water is slowly added, while ensureing that the temperature of solution is less than 40 DEG C；Hydrogen peroxide is added, continues to stir
15min；Last filtering drying obtains surface modified graphite alkene microplate；It is described that graphene-silicon is made in graphene-silica hybrid material
Nanometer powder composite is the 300-1000 DEG C of annealing 0.1-2h under inert atmosphere protection, obtains graphene-silicon nanopowder
Composite.
2. the method as described in claim 1, it is characterised in that described to prepare expanded graphite expansible graphite is placed in into metal
Or in ceramic crucible, under inert gas shielding, 300-900 degree is heated to, 10-60 points of keeping temperature realizes fully expansion,
Then it is cooled to room temperature.
3. the method as described in claim 1, it is characterised in that described to prepare expanded graphite expansible graphite is placed in into ceramics
In crucible or glassware, heated 10-60 seconds with 600-1200W microwaves, realize fully expansion, be then cooled to room temperature.
4. the method as described in claim 1, it is characterised in that it is described by obtained expanded graphite and organic solvent be mixed into by
Gained expanded graphite is placed in container, is poured into 100-1000ml organic solvents, is stirred.
5. method as claimed in claim 4, it is characterised in that the organic solvent is NMP, DMP, toluene, chlorobenzene and trichlorine
At least one of ethene.
6. the method as described in claim 1, it is characterised in that described that expanded graphite organic solvent mixed liquor is subjected to ultrasonic solution
It is to be vibrated under the conditions of sonic oscillation power is 300-1200W 1-24 hours from graphene microchip suspension is obtained, heats simultaneously
Temperature is 20-150 degree, obtains graphene microchip suspension.
7. the method as described in claim 1, it is characterised in that extract graphene microchip in the suspension from graphene microchip
For graphene microchip suspension obtained by ultrasound is stood into 0.2-5 hours, upper strata suspension is removed, sediment is removed, 80 after filtering
Spend in baking oven and dry.
8. the method as described in claim 1, it is characterised in that the graphene microchip for being modified surface mixes silicon nanometer
It is to add the surface modified graphite alkene microplate of gained in deionized water that grain, which obtains graphene-silica hybrid material, keeps solution
Temperature is less than 35 DEG C, ultrasonic disperse 10-60min；Nano silicon particles are added in deionized water, ultrasonic disperse 30-60min；
Nano silicon particles are easily mixed with surface modified graphite alkene solution, keep solution temperature to be less than 35 DEG C, ultrasonic disperse 30-
60min；Finally, solution is filtered out, surface modified graphite alkene-silica hybrid material is obtained.
9. the method as described in claim 1, it is characterised in that the making is based on graphene-silicon nano power powder composite material
Lithium battery cathode plate be using coating or roll pressure method, lithium battery cathode plate is made in metal foil substrate.
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| CN105742572A (en) * | 2014-12-12 | 2016-07-06 | 国家纳米科学中心 | Three-dimensional conductive network-supported porous silicon nanomaterial and preparation method and application thereof |
| CN107768608B (en) * | 2016-08-15 | 2020-10-16 | 福建新峰二维材料科技有限公司 | Preparation method of lithium ion battery cathode material capable of effectively buffering silicon volume effect |
| CN108017957A (en) * | 2016-11-03 | 2018-05-11 | 福建新峰二维材料科技有限公司 | A kind of preparation method of Graphene conductive ink applied to flexible circuit |
| CN106953088B (en) * | 2017-04-24 | 2020-08-18 | 广东烛光新能源科技有限公司 | Silicon-carbon negative electrode material and preparation method thereof |
| CN106920949B (en) * | 2017-04-24 | 2020-07-03 | 广东烛光新能源科技有限公司 | Silicon-carbon negative electrode material and preparation method thereof |
| CN108216384A (en) * | 2017-12-18 | 2018-06-29 | 合肥亿恒智能科技股份有限公司 | A kind of automobile rear floor front beam |
| CN111370665A (en) * | 2020-03-19 | 2020-07-03 | 西安越遴新材料研究院有限公司 | Preparation method of high-specific-capacity multi-sheet-layer stacked silicon-carbon composite material |
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