CN110048101A - A kind of silicon oxygen carbosphere composite negative pole material and the preparation method and application thereof - Google Patents
A kind of silicon oxygen carbosphere composite negative pole material and the preparation method and application thereof Download PDFInfo
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- CN110048101A CN110048101A CN201910264928.3A CN201910264928A CN110048101A CN 110048101 A CN110048101 A CN 110048101A CN 201910264928 A CN201910264928 A CN 201910264928A CN 110048101 A CN110048101 A CN 110048101A
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
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- 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
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
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- H—ELECTRICITY
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- 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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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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Abstract
The invention discloses a kind of silicon oxygen carbosphere composite negative pole material and preparation method thereof and purposes.The silicon oxygen carbosphere is core-shell structure, and diameter is 200~300nm.Preparation method is: the ethanol solution of silane is added in the mixed liquor of ethyl alcohol, deionized water and ammonium hydroxide and is stirred；Resorcinol and formaldehyde are added in above-mentioned mixed liquor and are stirred again；Then it is transferred in autoclave and reacts；It is cooled to room temperature, is washed after centrifuge separation with ethyl alcohol and deionized water, is then dried in vacuo, obtain silica/phenolic resin composite；By silica/phenolic resin composite high-temperature heat treatment, silicon oxygen carbosphere composite negative pole material can be obtained.Silicon oxygen carbosphere composite negative pole material of the invention is applied to lithium ion battery, can not only improve the coulombic efficiency for the first time and cycle life of lithium battery, and simple process, favorable reproducibility, easy to implement, suitable large-scale production.
Description
Technical field
The present invention relates to technical field of lithium ion battery negative more particularly to a kind of silicon oxygen carbosphere composite negative pole materials
Material and preparation method thereof.
Background technique
In recent years, it with the continuous development of lithium ion battery technology, is played more in the fields such as military affairs, space flight, civilian
Carry out more important role, is widely used in fields, the lithium ion battery demands such as electronic equipment, power vehicle and static energy storage and flies
Speed increases.Especially in the case where the policy that country greatly develops New-energy electric vehicle is inspired, the market access of lithium ion battery
Fast-developing channel, meanwhile, with the rapid development of new-energy automobile, it is necessary to increase substantially the energy of power lithium-ion battery
Metric density.Important component of the negative electrode material as lithium ion battery decides the performance and safety of lithium ion battery.Mesh
The capacity of preceding graphite carbons negative electrode material most widely used in the market is already close to its theoretical capacity 372mAh/g, room for promotion
Extremely limited, low capacity density seriously inhibits the extensive use of lithium ion battery.
Silicon based anode material is considered as next-generation lithium because of advantages such as its height ratio capacity (4200mAh/g), low de- lithium current potentials
The negative electrode material of the great application prospect of ion battery.However, big during the high production cost and removal lithium embedded of silicium cathode material
Volume change (300% or more) and lead to silicon particle dusting, fall off and capacity attenuation；Silicon particle surface solid electrolyte
(SEI) continued propagation of film limits it as cathode material to electrolyte and from factors such as the positive irreversible consumption of lithium source
The extensive use of material.On the other hand, the oxide of silicon such as aoxidizes sub- silicon (SiOx) compared to crystalline silicon nanoparticles, have more
More advantages, such as with high theoretical capacity (1500mAh/g or more)；Volume change is smaller in charge and discharge process, in charge and discharge
Silicon, Li can be generated in electric process2O and Li4Si4O4.Generated in-situ silicon is uniformly dispersed in Li2O and Li4Si4O4In matrix, both
The volume expansion during the embedding de- lithium of Si can be buffered to a certain extent, can also be prevented the reunion of Si particle, can also be buffered
Silicon lithium alloy volume change etc..Sub- silicon (SiO is aoxidized at presentx) negative electrode material is that industry thinks a new generation for being most hopeful industrialization
High capacity silicon based anode material.Although SiOxThere are these advantages, but SiOxLow conductivity and for the first time coulombic efficiency and do not allow to neglect
Depending on volume change limit its extensive use as negative electrode material in dynamic lithium battery field.In addition, being widely used at present
Commercial oxidation Asia silicon preparation condition strictly make its price relatively high.
For the these problems for aoxidizing sub- silicon (SiOx) negative electrode material, current main method of modifying is using ball milling, changes
It learns the methods of vapor deposition preparation and aoxidizes sub- silicon/carbon composite；But such methods complex process, and the cyclicity of material
It can be not high enough with coulombic efficiency for the first time.
Summary of the invention
In view of the above problems, an object of the present invention is to provide a kind of silicon oxygen carbosphere composite negative pole material.
In order to achieve the above-mentioned object of the invention, The technical solution adopted by the invention is as follows:
A kind of silicon oxygen carbosphere composite negative pole material, by silane, resorcinol, formaldehyde, ethyl alcohol, ammonium hydroxide and deionized water system
It is standby to form；The diameter of the silicon oxygen carbosphere is 200~300nm, and the structure of the microballoon is to aoxidize outside sub- silicon kernel-carbon
Shell, the carbon shell with a thickness of 20-80nm.
Preferably, the silane is in four (2- methoxy ethoxy) silane, tetramethoxy-silicane and tetraethoxysilanes
One or more kinds of mixtures.
The second object of the present invention is to provide a kind of preparation method of above-mentioned silicon oxygen carbosphere composite negative pole material.Specific skill
Art scheme is as follows:
A kind of preparation method of above-mentioned silicon oxygen carbosphere composite negative pole material, specifically includes the following steps:
(1) silane is added to stirring in ethyl alcohol until all dissolving, the concentration of silane in ethanol is 0.05~0.1g/
L obtains solution A；
(2) ammonium hydroxide that ethyl alcohol, deionized water and concentration are 25~28% is mixed according to volume ratio 1.5~3:1:0.5~0.8
Merging stirs evenly, and obtains solution B；
(3) step (1) acquired solution A is added in step (2) acquired solution B according to volume ratio 1:1 and stirs 1~3
Hour, obtain solution C；
(4) formaldehyde that resorcinol and concentration are 36~38wt% is added in step (3) acquired solution C and stirs 24
~36 hours, concentration of the resorcinol in solution C was 6.25~17.5g/L, the matter of the resorcinol and formaldehyde
Amount is than being 2.05~2.82:1；Then it is transferred in autoclave and is kept for 20~30 hours at 90~110 DEG C；Then it is cooled to
Room temperature is centrifuged with the revolving speed of 5000~8000r/min, then that gained sediment ethyl alcohol and deionized water is successive
Washing 2~3 times, then be dried in vacuo 20~30 hours under the conditions of 70~90 DEG C, obtain silica/phenolic resin composite；
(5) silica/phenolic resin composite described in step (4) is placed in tube furnace, and to tube furnace
In be passed through the nitrogen argon mixture gas of nitrogen or argon gas or arbitrary proportion, be warming up under atmosphere protection with the rate of 2~5 DEG C/min
800-1100 DEG C and holding 3~5 hours, cooled to room temperature, obtains the silicon oxygen carbosphere composite negative pole material later.
The third object of the present invention is to provide the application of above-mentioned silicon oxygen carbosphere composite negative pole material.Specific technical solution is such as
Under:
The silicon oxygen carbosphere composite negative pole material is applied to the cathode of lithium ion battery.
Preferably, it is applied particularly to CR2032 fastening lithium ionic cell, application method is as follows:
(A) by silicon oxygen carbosphere composite negative pole material, conductive agent Super P, binder Kynoar according to mass ratio
7:2:1 is uniformly mixed, and obtains solid mixture；
(B) solid mixture that step (A) obtains is mixed with N-Methyl pyrrolidone, wherein the solid mixes
Object accounting is 18~25wt%, and slurry is made after mixing evenly；
(C) slurry for obtaining step (B) is coated on copper foil, is made after drying, roll-in with a thickness of 13~23 μm
Lithium ion cell electrode piece；
(D) the lithium ion cell electrode piece for obtaining step (C) is as Electrode Negative piece, lithium piece as electrode anode piece,
Use microporous polypropylene membrane for diaphragm, using the LiPF of 1mol/L6And solvent is electrolyte, is filled in the glove box full of argon gas
It is made into CR2032 fastening lithium ionic cell.
Preferably, solvent described in step (D) is the mixture of isometric dimethyl carbonate and dipropyl carbonate.
The advantages of the present invention:
On the one hand silicon oxygen carbosphere prepared by the present invention can alleviate oxygen as lithium ion battery negative material, the presence of carbon
Change volume change of the sub- silicium cathode material in charge and discharge process, also advantageously improves the conductivity of material on the other hand to change
Kind high rate performance not only increases the coulombic efficiency for the first time (reaching 80% or so) and cycle life (circulation 100 times of lithium battery
Afterwards, capacity retention ratio be more than 86%), and it is simple process, favorable reproducibility, easy to implement, be suitble to large-scale production.It can apply
In lithium ion batteries such as CR2032 fastening lithium ionic cells.
Detailed description of the invention
Fig. 1 is the XRD of silicon oxygen carbon (SiOx/C) micro-sphere compound anode material prepared by the embodiment of the present invention 1.
Fig. 2 is the scanning electron microscope (SEM) photograph of silicon oxygen carbosphere composite negative pole material prepared by the embodiment of the present invention 1.
Specific embodiment
In order to make the objectives, technical solutions, and advantages of the present invention clearer, with reference to the accompanying drawings and embodiments, right
The present invention is described in further detail.It should be appreciated that specific embodiment described herein is used only for explaining the present invention,
It is not intended to limit the present invention.
Embodiment 1
A kind of preparation method of silicon oxygen carbosphere composite negative pole material, the specific steps are as follows:
(1) 3.0mg tetraethoxysilane is added to stirring in 30mL ethyl alcohol until all dissolving, obtains solution A；
(2) it by 20mL ethyl alcohol, 12mL deionized water and 8mL ammonium hydroxide (36~38wt%), is mixed and stirred for uniformly, obtaining molten
Liquid B；
(3) step (1) acquired solution A is added in step (2) acquired solution B according to volume ratio 1:1 and stirs 1~3
Hour, obtain solution C；
(4) by 1.04g resorcinol and 1.69mL formaldehyde (mass fraction: 36~38%；Density: 0.82g/ml) it is added to
It in step (3) acquired solution C and stirs 24~36 hours, be then transferred in autoclave at 100 DEG C and kept for 20 hours；
It is then cooled to room temperature, is centrifuged with the revolving speed of 5000r/min；Then by gained sediment ethyl alcohol and deionized water
Successively washing 3 times, are then dried in vacuo 20 hours under the conditions of 70 DEG C again, obtain silica/phenolic resin composite；
(5) silica/phenolic resin composite described in step (4) is placed in tube furnace, and to tube furnace
In be passed through nitrogen, under atmosphere protection with the rate of 2 DEG C/min be warming up to 1100 DEG C and keep 3 hours, naturally cool to later
Room temperature obtains silicon oxygen carbosphere composite negative pole material.The diameter of thus obtained microsphere about 250nm is presented and is aoxidized sub- silicon kernel-carbon shell
Core-shell structure, the thickness of carbon shell is in 20~50nm or so, as shown in Figure 1.
(6) assembling and performance test of lithium ion battery: according to mass ratio 70:20:10 by silicon oxygen carbosphere composite negative pole
Material, conductive agent Super P and binder Kynoar are after mixing；It will after mixing according still further to mass ratio 20:80
Solid mixture (mixture of silicon oxygen carbosphere composite negative pole material, Super P and Kynoar) and N- methylpyrrole
Alkanone is mixed and stirred for that slurry is uniformly made；Slurry is coated on copper foil later, be made after drying, roll-in with a thickness of 13~
23 μm of lithium ion cell electrode negative electrode tab.Then using lithium piece as electrode anode piece, microporous polypropylene membrane is diaphragm, 1mol/L
LiPF6(solvent is isometric dimethyl carbonate and dipropyl carbonate) is electrolyte, is being full of argon gas with this Electrode Negative piece
Glove box in be assembled into CR2032 fastening lithium ionic cell.After lithium ion battery is stood 24 hours, respectively in 0.1C electric current
Lower carry out charge-discharge test, charge and discharge voltage is between 0.01~3.0V.
The results are shown in Table 1 for the lithium electrical property of the present embodiment.
Embodiment 2
(1) 1.54mg tetramethoxy-silicane is added to stirring in 30mL ethyl alcohol until all dissolving, obtains solution A；
(2) it by 20mL ethyl alcohol, 12mL deionized water and 8mL ammonium hydroxide (36~38wt%), is mixed and stirred for uniformly, obtaining molten
Liquid B；
(3) step (1) acquired solution A is added in step (2) acquired solution B according to volume ratio 1:1 and stirs 1~3
Hour, obtain solution C；
(4) by 0.39g resorcinol and 0.58mL formaldehyde (mass fraction: 36~38%；Density: 0.82g/ml) it is added to
It in step (3) acquired solution C and stirs 24~36 hours, be then transferred in autoclave at 100 DEG C and kept for 20 hours；
It is then cooled to room temperature, is centrifuged with the revolving speed of 5000r/min；Then by gained sediment ethyl alcohol and deionized water
Successively washing 3 times, are then dried in vacuo 20 hours under the conditions of 70 DEG C again, obtain silica/phenolic resin composite；
(5) silica/phenolic resin composite described in step (4) is placed in tube furnace, and to tube furnace
In be passed through nitrogen, under atmosphere protection with the rate of 2 DEG C/min be warming up to 1000 DEG C and keep 3 hours, naturally cool to later
Room temperature obtains silicon oxygen carbosphere composite negative pole material.
(6) assembling and performance test of lithium ion battery: according to mass ratio 70:20:10 by silicon oxygen carbosphere composite negative pole
Material, conductive agent Super P and binder Kynoar are after mixing；It will after mixing according still further to mass ratio 20:80
Solid mixture (mixture of silicon oxygen carbosphere composite negative pole material, Super P and Kynoar) and N- methylpyrrole
Alkanone is mixed and stirred for that slurry is uniformly made；Slurry is coated on copper foil later, be made after drying, roll-in with a thickness of 13~
23 μm of lithium ion cell electrode negative electrode tab.Then using lithium piece as electrode anode piece, microporous polypropylene membrane is diaphragm, 1mol/L
LiPF6(solvent is isometric dimethyl carbonate and dipropyl carbonate) is electrolyte, is being full of argon gas with this Electrode Negative piece
Glove box in be assembled into CR2032 fastening lithium ionic cell.After lithium ion battery is stood 24 hours, respectively in 0.1C electric current
Lower carry out charge-discharge test, charge and discharge voltage is between 0.01~3.0V.
The results are shown in Table 1 for the lithium electrical property of the present embodiment.
Embodiment 3
(1) 2.1mg tetra- (2- methoxy ethoxy) silane is added to stirring in 30mL ethyl alcohol until all dissolving, obtained
Solution A；
(2) it by 20mL ethyl alcohol, 12mL deionized water and 8mL ammonium hydroxide (36~38wt%), is mixed and stirred for uniformly, obtaining molten
Liquid B；
(3) step (1) acquired solution A is added in step (2) acquired solution B according to volume ratio 1:1 and stirs 1~3
Hour, obtain solution C；
(4) by 0.62g resorcinol and 0.72mL formaldehyde (mass fraction: 36~38%；Density: 0.82g/ml) it is added to
It in step (3) acquired solution C and stirs 24~36 hours, be then transferred in autoclave at 100 DEG C and kept for 20 hours；
It is then cooled to room temperature, is centrifuged with the revolving speed of 5000r/min；Then by gained sediment ethyl alcohol and deionized water
Successively washing 3 times, are then dried in vacuo 20 hours under the conditions of 70 DEG C again, obtain silica/phenolic resin composite；
(5) silica/phenolic resin composite described in step (4) is placed in tube furnace, and to tube furnace
In be passed through nitrogen, under atmosphere protection with the rate of 2 DEG C/min be warming up to 800 DEG C and keep 3 hours, naturally cool to room later
Temperature obtains silicon oxygen carbosphere composite negative pole material.
(6) assembling and performance test of lithium ion battery: according to mass ratio 70:20:10 by silicon oxygen carbosphere composite negative pole
Material, conductive agent Super P and binder Kynoar are after mixing；It will after mixing according still further to mass ratio 20:80
Solid mixture (mixture of silicon oxygen carbosphere composite negative pole material, Super P and Kynoar) and N- methylpyrrole
Alkanone is mixed and stirred for that slurry is uniformly made；Slurry is coated on copper foil later, be made after drying, roll-in with a thickness of 13~
23 μm of lithium ion cell electrode negative electrode tab.Then using lithium piece as electrode anode piece, microporous polypropylene membrane is diaphragm, 1mol/L
LiPF6(solvent is isometric dimethyl carbonate and dipropyl carbonate) is electrolyte, is being full of argon gas with this Electrode Negative piece
Glove box in be assembled into CR2032 fastening lithium ionic cell.After lithium ion battery is stood 24 hours, respectively in 0.1C electric current
Lower carry out charge-discharge test, charge and discharge voltage is between 0.01~3.0V.
The results are shown in Table 1 for the lithium electrical property of the present embodiment.
Table 1 is that the lithium ion battery of Examples 1 to 3 carries out charge-discharge test first lap and the 100th circle under 0.1C electric current
Capacity obtained.
Table 1
As it can be seen from table 1 lithium ion battery is applied to as electrode anode material using silicon oxygen carbosphere of the invention,
Charging capacity has good cycle performance 86% or more in 896mAh/g or more, capacity retention ratio after the circle of circulation 100,
Still it is much higher than the graphite cathode material of Current commercial.
The foregoing is intended to be a preferred embodiment of the present invention.Certainly, the present invention can also have other a variety of implementations
Example, without deviating from the spirit and substance of the present invention, anyone skilled in the art, when can according to this
Various corresponding equivalent change and modification are made in invention, all should fall within the scope of protection of the appended claims of the present invention.
Claims (6)
1. a kind of silicon oxygen carbosphere composite negative pole material, which is characterized in that by silane, resorcinol, formaldehyde, ethyl alcohol, ammonium hydroxide and
Deionized water is prepared；The silicon oxygen carbosphere is to aoxidize sub- silicon kernel-carbon shell mechanism, a diameter of 200~
300nm, carbon shell with a thickness of 20-80nm.
2. silicon oxygen carbosphere composite negative pole material according to claim 1, which is characterized in that the silane is four (2-
Methoxy ethoxy) one of silane, tetramethoxy-silicane and tetraethoxysilane or any mass ratio a variety of mixtures.
3. a kind of preparation method of silicon oxygen carbosphere composite negative pole material as claimed in claim 2, which is characterized in that specific packet
Include following steps:
(1) silane is added to stirring in ethyl alcohol until all dissolving, the concentration of silane in ethanol is 0.05~0.1g/L, is obtained
To solution A；
(2) ammonium hydroxide that ethyl alcohol, deionized water and concentration are 25~28% is mixed simultaneously according to 1.5~3:1:0.5 of volume ratio~0.8
It stirs evenly, obtains solution B；
(3) step (1) acquired solution A is added in step (2) acquired solution B and is stirred 1~3 hour according to volume ratio 1:1,
Obtain solution C；
(4) formaldehyde that resorcinol and concentration are 36~38wt% is added in step (3) acquired solution C and stirs 24~36
Hour, concentration of the resorcinol in solution C is 6.25~17.5g/L, the mass ratio of the resorcinol and formaldehyde
For 2.05~2.82:1；Then it is transferred in autoclave and is kept for 20~30 hours at 90~110 DEG C；Then it is cooled to room
Temperature is centrifuged with the revolving speed of 5000~8000r/min, then successively washes gained sediment ethyl alcohol and deionized water
It washs 2~3 times, then is dried in vacuo 20~30 hours under the conditions of 70~90 DEG C, obtain silica/phenolic resin composite；
(5) silica/phenolic resin composite described in step (4) is placed in tube furnace, and led into tube furnace
The nitrogen argon mixture gas for entering nitrogen or argon gas or arbitrary proportion, is warming up to 800- under atmosphere protection with the rate of 2~5 DEG C/min
1100 DEG C and holding 3~5 hours, cooled to room temperature, obtains the silicon oxygen carbosphere composite negative pole material later.
4. the cathode that a kind of silicon oxygen carbosphere composite negative pole material as claimed in claim 2 is applied to lithium ion battery.
5. the method applied according to claim 4 is specifically applied to CR2032 fastening lithium ionic cell, it is characterised in that
Include the following steps:
(A) by silicon oxygen carbosphere composite negative pole material, conductive agent Super P, binder Kynoar according to mass ratio 7:2:1
It is uniformly mixed, obtains solid mixture；
(B) solid mixture that step (A) obtains is mixed with N-Methyl pyrrolidone, wherein the solid mixture accounts for
Than slurry being made after mixing evenly for 18~25wt%；
(C) slurry for obtaining step (B) be coated in copper foil on, after drying, roll-in be made with a thickness of 13~23 μm lithium from
Sub- battery electrode piece；
(D) the lithium ion cell electrode piece for obtaining step (C) is used as Electrode Negative piece, lithium piece as electrode anode piece
Microporous polypropylene membrane is diaphragm, using the LiPF of 1mol/L6And solvent is electrolyte, is assembled into the glove box full of argon gas
CR2032 fastening lithium ionic cell.
6. according to the method described in claim 5, it is characterized in that, solvent described in step (D) is isometric carbonic acid diformazan
The mixture of ester and dipropyl carbonate.
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| CN110756177B (en) * | 2019-10-24 | 2022-08-30 | 齐鲁工业大学 | Preparation method and application of functionalized nano silicon dioxide/resorcinol-formaldehyde microspheres |
| CN111509212A (en) * | 2020-04-30 | 2020-08-07 | 厦门高容纳米新材料科技有限公司 | Silicon-carbon composite negative electrode material, negative electrode plate, preparation method of negative electrode plate and lithium ion battery |
| CN111509212B (en) * | 2020-04-30 | 2022-07-01 | 厦门高容纳米新材料科技有限公司 | Silicon-carbon composite negative electrode material, negative electrode plate, preparation method of negative electrode plate and lithium ion battery |
| CN111600005B (en) * | 2020-06-16 | 2022-04-22 | 广西师范大学 | Preparation method of lithium ion battery negative electrode material porous Si/C composite material |
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| CN112310386A (en) * | 2020-11-02 | 2021-02-02 | 哈尔滨工业大学 | Silicon oxide/carbon lithium ion battery cathode material with hollow structure and preparation method and application thereof |
| CN112310386B (en) * | 2020-11-02 | 2021-12-28 | 哈尔滨工业大学 | Silicon oxide/carbon lithium ion battery cathode material with hollow structure and preparation method and application thereof |
| CN112652758A (en) * | 2020-12-14 | 2021-04-13 | 云帆(镇江)新能源材料有限公司 | Silicon oxide/carbon microsphere composite negative electrode material for lithium ion battery and preparation method thereof |
| CN113213493A (en) * | 2021-04-13 | 2021-08-06 | 武汉纽赛儿科技股份有限公司 | Pomegranate-shaped silicon oxide-nitrogen-doped carbon composite material, synthetic method thereof and lithium ion capacitor |
| CN113213493B (en) * | 2021-04-13 | 2023-05-26 | 武汉纽赛儿科技股份有限公司 | Granati-shaped silicon oxide-nitrogen doped carbon composite material, synthesis method thereof and lithium ion capacitor |
| CN113611864A (en) * | 2021-07-30 | 2021-11-05 | 江苏泛亚微透科技股份有限公司 | Carbon aerogel coated silica hollow microsphere negative electrode material |
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| CN114122370A (en) * | 2021-10-29 | 2022-03-01 | 西安交通大学 | Negative electrode material for inducing silane deposition through porous carbon double bond modification and preparation method and application thereof |
| CN114122370B (en) * | 2021-10-29 | 2023-12-19 | 西安交通大学 | Porous carbon double bond modified silane deposition-induced negative electrode material and preparation method and application thereof |
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