CN109950492A - A kind of method of In-situ reaction preparation lithium ion battery carbon silicon anode material - Google Patents
A kind of method of In-situ reaction preparation lithium ion battery carbon silicon anode material Download PDFInfo
- Publication number
- CN109950492A CN109950492A CN201910231092.7A CN201910231092A CN109950492A CN 109950492 A CN109950492 A CN 109950492A CN 201910231092 A CN201910231092 A CN 201910231092A CN 109950492 A CN109950492 A CN 109950492A
- Authority
- CN
- China
- Prior art keywords
- graphene oxide
- lithium ion
- ion battery
- anode material
- silicon
- 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
Classifications
-
- 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
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a kind of methods of In-situ reaction preparation lithium ion battery carbon silicon anode material to obtain suspension by using graphene oxide as carbon source, taking graphene oxide and the churned mechanically mode of silicon nano；Ascorbic acid is added in suspension and stirs evenly, is warming up to 50-80 DEG C, ascorbic acid restores graphene oxide, is precipitated together with the silicon nano coated with it and is washed, dries to obtain product.The silicon nano and the compound negative electrode material of graphene of this patent can not only overcome the serious defect of silicon based anode material volume expansion, the excellent electricity of graphene, calorifics and mesoscopic structure characteristic can more be played, while realizing high energy density, it realizes good charge-discharge performance and cycle performance, becomes next-generation negative electrode of lithium ion battery critical material.Simultaneous oxidation graphene good water solubility, preparation process water solution system, reducing agent is nontoxic, at low cost, and reaching entire reduction process, low energy consumption, and post-reaction treatment process is simple.
Description
Technical field
The present invention relates to lithium ion battery negative material, specifically a kind of In-situ reaction prepares lithium ion battery carbon silicon anode
The method of material.
Background technique
Lithium ion battery as a kind of novel electrochmical power source, because its output voltage is high, specific energy is high, have extended cycle life,
Self discharge is small, safety, memory-less effect and the environmental-friendly weight for having become our times various countries and developing in new energy materials field
Point.Electrode material is the principal element for influencing battery performance and cost, and research and development electrode material has the development of lithium battery
Significance.For lithium ion battery, the performance of positive and negative pole material can directly determine the performance of battery.In negative electrode material side
Face.Elemental silicon receives more and more attention due to very high theoretical specific capacity as negative electrode material, it is considered as
One of the material of most possible substitution graphite cathode, however silicon-based anode is not put into commercially use slowly but.This be because
About 300% volume expansion/contraction can be generated during Li insertion extraction for silicon, huge volume change will cause silicon electrode
Dusting is peeled off, and makes to lose electrical contact between silicon particle and between silicon and collector, and the specific capacity of electrode sharply declines even complete
Full failure).In general, the reversible specific capacity of common pure silicon cathode can be dropped to from 3000mAh/g in 5 circulations it is almost nil.
The key that graphene is succeeded in practical applications is that the producer of lot of materials can be provided with low cost
Method.In this respect, the method (i.e. the micromechanics cracking of graphite) for causing graphene to separate first is a kind of low-yield, small throughput
Technique, be therefore less likely to it is industrially expansible, this make find substitution preparation techniques it is preferential.Colloid route is presently considered to
It is the most attractive selection of many other desired uses of graphene.The major advantage of this route is cost-effectiveness, greatly
The scalability of scale, the multifunctionality of chemistry functional, and be easily processed into paper-like material, coating, composite material etc..
It is usually directed to by the soliquid of graphite oxide production graphene in suitable solvent (usually water, also one
A little polar organic solvents) in the latter is removed, then with hydrazine electronation disperse single-layer sheet (graphene oxide sheet).Work as reduction
When carrying out under controlled conditions, resulting deoxidation graphene oxide sheet formed stable suspension without surfactant or
Any other stabilizer, this is an additional advantage.Unfortunately, hydrazine is a kind of hypertoxic and has potential volatile chemistry
Substance, therefore should be avoided when implementing this method on a large scale and use it.
Then silicon powder and graphite mixing and ball milling are added pitch or poly- by the prior art such as patent CN200810031840.9
Close object covering material ball milling again, carbonization treatment, after crushed, obtain a kind of clang ion battery silicon with one nuclear structure of shell
Carbon compound cathode materials, center are elemental silicon and graphite, and shell is the pyrolytic carbon of pitch or polymer overmold material, this method
It is after silicon powder and the mixing of carbon or silicon carbide, direct ball milling is at nanocomposite.Silicon powder and carbon material pass through high energy mechanical ball
It, can be mutually evenly dispersed with nanoscale after mill.Due to surrounding carbon material around the silicon powder of nano-scale, so as to press down
System improves the cycle performance of silicon materials due to inserting volume change caused by lithium and de- lithium to a certain extent.With silicone content
Increase, silicon/carbon composite specific capacity increases, but cyclical stability is deteriorated.Meanwhile in composite material two kinds of components crystal
Structure and size and compatibility decide the final performance of material.The main problems of the composite materials prepared by this method are as follows:
Since specific surface area is larger, and the micro-oxidation in mechanical milling process cannot be entirely prevented, therefore irreversible capacity is big for the first time.
104681787 A of CN discloses the lithium ion battery self-supporting silicon based anode material and its system of a kind of plural layers
Preparation Method.The preparation method the following steps are included: the mixture for first forming nano silicon particles/organic high molecular polymer with
Organic high molecular polymer disperses in organic solvent, to be sufficiently stirred respectively, respectively obtains uniform suspension and solution；It connects down
Carbonization treatment is carried out under protective atmosphere, that is, prepares the lithium ion battery self-supporting silicon-based anode material with plural layers
Material.This method can be well dispersed in silicon powder in carbon matrix, improve its cycle performance；But due to shape after high polymer carbonization
At be amorphous carbon, the stability and electric conductivity of graphitic carbon material cannot be embodied completely, and may be due to amorphous structure
And increase the irreversible capacity for the first time of composite material, therefore comprehensive performance is unsatisfactory.
102013487 A of CN provides a kind of lithium ion battery negative material, is by pitch or resin and silicone resin or silicon
Glue and magnesium powder after mixing, obtain after Overheating Treatment is using cleaning treatment.Wherein, silicon is dispersed in carbon base body,
It is to react receiving of being formed in situ with magnesium powder during heat treatment containing silicon precursor selected from silicone resin, silica gel by one or more of
Rice grain.Carbon is by being by one or more selected from coal tar pitch, petroleum residual oil pitch, coal tar, mesophase pitch, phenolic resin
Containing carbon matrix precursor by carbonization heat treatment formed.Pitch not only can be used as binder and uniformly combine graphite and silicon, and
The effect of surface covering is also acted as after carbonization.But pitch low-temperature carbonization product is similarly amorphous structure, and pitch is as viscous
Knot agent material property limited to the cementation of carbon and silicon therefore prepared needs to be further increased.
108565408 A of CN discloses a kind of lithium ion battery negative material and preparation method thereof and uses carbon-silico-carbo three
The structure of layer three-dimensional globular, most one layer of the inside are graphitic carbon, swollen for providing volume of silicon during insertion/deintercalate lithium ions
Swollen space；Intermediate one layer is amorphous silicon, is used to receive the lithium ion to come from anode migration as cathode, realizes energy storage；Most
Outer one layer deposits carbon for pyrolytic carbon or PECVD, for providing stable skeleton structure, to guarantee silicon in the process for expanding and reducing
The stability of middle cathode entirety, the generation for phenomena such as preventing dusting and fall off from microcosmic.Directly utilize CVD method, to silicon or
Silicon/carbon mix carries out carbon film package.After coating, the cycle performance of silicon improves, but since coating amount is less, cannot embody completely
Carbon base body effect, prepared material property is poor, but the material prepared by this method can study silicon/carbon composite
Store up lithium mechanism.
In short, gained carbon silicon materials are difficult have cyclical stability on the basis of keeping high specific capacitance in the prior art
Good and fast transmission rate.
Summary of the invention
The technical problem to be solved by the present invention is in view of the deficiencies of the prior art, to the carbon source and system of carbon silicium cathode material
Standby process improves, and a kind of method of In-situ reaction preparation lithium ion battery carbon silicon anode material is provided, so that preparing carbon
Silicium cathode materials process is nontoxic, at low cost, low energy consumption, post-reaction treatment process is simple, obtained battery carbon silicium cathode material
Material has good cycling stability and fast transmission rate on the basis of keeping high specific capacitance.
In order to solve the above-mentioned technical problem, the technical solution adopted by the present invention is as follows:
A kind of method of In-situ reaction preparation lithium ion battery carbon silicon anode material, includes the following steps:
(1) prepared by graphene oxide: natural graphite powder being pre-processed using dilute hydrochloric acid, is then added to 0~3 DEG C of dense sulphur
In acid, NaNO is sequentially added under stirring3And KMnO4, and continue to be stirred to react 2~3h, until being moved after solution is in blackish green
Enter to continue to be stirred to react in 30 DEG C of constant water bath box to solution and becomes pink by blackish green；Then add concentrated sulfuric acid solution simultaneously
1~2h is stirred, after solution is in bronzing, stirring 1h is further continued for and H is then added2O2Solution, after solution becomes golden yellow again
2h is stirred, is filtered while hot, product dilute hydrochloric acid solution and deionized water are washed repeatedly until sulfate radical-free ion in filtrate,
After drying to obtain the final product；
(2) prepared by graphene oxide sheet suspension: the graphene oxide that step (1) obtains first is ultrasonically treated in a solvent
Then 1~2h turns/min with 5000-10000, be centrifuged 5-10min to remove unstripped substance, separation supernatant is aoxidized
Graphene film suspension；
(3) prepared by carbon silicium cathode material: silicon nano is added to the graphene oxide sheet suspension that step (2) obtains
In, and being sufficiently stirred makes it be uniformly dispersed, and reducing agent ascorbic acid is then added, is warming up to 50-80 DEG C, is stirred to react 60-
Then 600min is spray-dried to obtain the composite material of graphene and silicon, subsequent cooled to room temperature to obtain the final product.
When finding the substitute of hydrazine, other than environmental and safety problems, it is also contemplated that two correlative factors.Firstly, should
Method should be effective at least as hydrazine in the deoxidation of graphene oxide.Second, in order to be further processed, reducing material be should be used as
Single sheet remains dispersed in aqueous and organic media, that is to say, that it should not be precipitated after reduction.
Ascorbic acid is many essential naturals of metabolic function in organism, is widely used as food addition
Agent.It can not only be prepared, but also can be prepared in some common organic solvents, such as N in water with ascorbic acid reduction,
Dinethylformamide (DMF) and n-methyl-2-pyrrolidone (NMP).The nontoxicity of these discoveries and this natural products
Show that ascorbic acid is the ideal substitute of hydrazine in the graphene for be mass produced solution processable.So that the present invention prepares carbon
Silicium cathode materials process is nontoxic, at low cost, and reaching entire reduction process, low energy consumption, and post-reaction treatment process is simple.
Specifically, in step (1), the natural graphite powder, the concentrated sulfuric acid, NaNO3And KMnO4Amount ratio be 2-6g:300-
350ml:3.5-5g:20-25g.
Preferably, the concentrated sulfuric acid solution concentration added is 98wt%, and dosage is 20-40ml/5g natural graphite powder；
The H2O2Solution concentration is 30wt%, and dosage is 10-40ml/5g natural graphite powder.Wherein, the concentrated sulfuric acid aoxidizes stone for intercalation
Ink, hydrogen peroxide are to be used to react away excess sulfuric acid under the premise of not introducing new ion.
In step (2), the solvent is water or ethyl alcohol.
In obtained graphene oxide sheet suspension, graphene oxide layer is having a size of 1-10nm, graphene oxide sheet
Concentration is 0.1-2mg/mL.
In step (3), the grain diameter of the silicon nano is 1-50nm, has good monodispersity；With nanometer
The silicon particle of size is raw material, can reduce the absolute volume variation degree of silicon, while also can be shortened lithium ion and electronics
Diffusion length improves electric conductivity.
Preferably, the mass ratio of graphene oxide sheet and silicon nano is 1 in the graphene oxide sheet suspension:
0.2-1:2。
The mass ratio of graphene oxide sheet and reducing agent ascorbic acid is 1:0.35- in the graphene oxide sheet suspension
3.5。
The inlet temperature of the spray drying is 180-220 DEG C, and outlet temperature is 90-130 DEG C.
In carbon silicium cathode material prepared by the present invention, the electric conductivity of carbon material is preferable, can overcome the disadvantages that silicon materials poorly conductive
Disadvantage improves the electric conductivity of silicon based anode material；On the other hand, carbon material during embedding de- lithium volume change very little (<
10%), and carbon material usually has good lubricity, and the carbon cushioning frame being made of it can effectively inhibit/alleviate silicon to exist
Stereomutation during Li insertion extraction maintains electrode structure and electric conductivity well, so that silica-base material follows
Ring stability improves.In addition, carbon material itself both can increase the ratio of composite material also with the activity of reversible Li insertion extraction in this way
Capacity can accelerate the transmission rate of lithium ion in the composite again.
The utility model has the advantages that
The present invention improves the carbon source and preparation process of carbon silicium cathode material, obtain a kind of In-situ reaction prepare lithium from
The method of sub- battery carbon silicium cathode material.This method is by taking graphene oxide and silicon nanometer using graphene oxide as carbon source
The churned mechanically mode of particle, obtains suspension；Ascorbic acid is added in suspension and stirs evenly, is warming up to 50-80 DEG C, resists
Bad hematic acid restores graphene oxide, is precipitated together with the silicon nano coated with it；Silicon-carbon nanoparticle is obtained after washing several times
Son, drying obtain product.The silicon nano and the compound negative electrode material of graphene of this patent can not only overcome silicon-based anode
Material volume expands serious defect, can more play the excellent electricity of graphene, calorifics and mesoscopic structure characteristic, realize
While high energy density, realizes good charge-discharge performance and cycle performance, become next-generation negative electrode of lithium ion battery
Critical material.Simultaneous oxidation graphene good water solubility, preparation process water solution system, reducing agent is nontoxic, at low cost, reaches
Low energy consumption for entire reduction process, and post-reaction treatment process is simple.
Specific embodiment
According to following embodiments, the present invention may be better understood.
In following embodiment, natural graphite powder is purchased from Qingdao Rui Sheng graphite Co., Ltd, 0.5-10 μm of lamella diameter.Silicon is received
Rice corpuscles grain diameter is 1-50nm, purifies Science and Technology Ltd. purchased from Hangzhou intelligence titanium.
Embodiment 1:
Three steps are broadly divided into using the process that improved Hummers method prepares graphite oxide:
A. low-temp reaction: firstly, the 325ml concentrated sulfuric acid (H is added into beaker2SO4), and flask is put into cryostat
In, temperature is controlled at 0~3 DEG C；It is added and uses dilute hydrochloric acid (HCl) processed natural graphite powder 5g in advance, be slow added into
3.75g NaNO3, it is stirring while adding, it is slow added into 22.5g potassium permanganate (KMnO4) (about 1h is added), it is stirred to react 2h, this
When solution in blackish green；
B. medium temperature is reacted: and then by 30 DEG C of flask immigration of constant water bath box, continue to be stirred to react a couple of days, at this time solution
Become pink by blackish green；.
C. pyroreaction: it is then slowly added to 25.5ml 98%H2SO4+H2O continues stir about 1h, and solution is in red at this time
Brown continues to stir 1h, is finally slowly added to 15ml 30%H2O2, solution becomes golden yellow at this time, continues to stir 2h, while hot mistake
Filter, and the hydrochloric acid and deionized water that are 5% with mass fraction are washed repeatedly until sulfate radical-free ion in filtrate, will be filtered
Product afterwards, which is placed in 50 DEG C of vacuum ovens, sufficiently to be dried, and is saved backup；
Suspension in given solvent (usually water), by graphite oxide object slurry obtained above or dry powder in solvent
Middle bath is ultrasonically treated 1 hour, then turns centrifugation 5-10min with 5000-10000 to remove unstripped substance, supernatant is most
Whole graphene oxide sheet suspension is 0.1-2mg/ using the concentration for measuring suspension by UV-Vis Spectrophotometry
mL。
0.2g silicon nano (average grain diameter 10nm) is added to the above-mentioned graphene oxide sheet suspension (piece of 100mL
Layer size 5nm) in, so that it is uniformly dispersed in 200rpm mechanical stirring 60min, 0.2g reducing agent ascorbic acid is added, is warming up to
80 DEG C, stir 300min, be added and then be spray-dried, inlet temperature at 200 DEG C, outlet temperature at 110 DEG C, go from
Sub- water obtains the composite material of graphene and silicon；Then cooled to room temperature obtains carbon in lithium ion battery silicon composite cathode material
Material.As lithium ion battery negative material, it is packaged into button cell with positive electrode, diaphragm, electrolyte tabletting, measurement is first
Secondary discharge capacity is 1800mAh/g.
Embodiment 2:
Graphene oxide sheet suspension preparation process is same as Example 1；
0.1g silicon nano (average grain diameter 30nm) is added to the above-mentioned graphene oxide sheet suspension (piece of 100mL
Layer size 10nm) in, so that it is uniformly dispersed in 200rpm mechanical stirring 60min, 0.5g reducing agent ascorbic acid is added, is warming up to
80 DEG C, stir 180min, be added and then be spray-dried, inlet temperature at 180 DEG C, outlet temperature at 90 DEG C, go from
Sub- water obtains the composite material of graphene and silicon；Then cooled to room temperature obtains carbon in lithium ion battery silicon composite cathode material
Material.As lithium ion battery negative material, it is packaged into button cell with positive electrode, diaphragm, electrolyte tabletting, is filled for the first time
Discharge capacity 1830mAh/g.
Embodiment 3:
Graphene oxide sheet suspension preparation process is same as Example 1；
0.4g silicon nano (average grain diameter 10nm) is added to the above-mentioned graphene oxide suspension (lamella of 100mL
Size 5nm) in, so that it is uniformly dispersed in 250rpm mechanical stirring 60min, 0.5g reducing agent ascorbic acid is added, is warming up to 80
DEG C, 240min is stirred, is added and then is spray-dried, for inlet temperature at 220 DEG C, outlet temperature removes deionization at 130 DEG C
Water obtains the composite material of graphene and silicon；Then cooled to room temperature obtains carbon in lithium ion battery silicon composite cathode material
Material.As lithium ion battery negative material, it is packaged into button cell with positive electrode, diaphragm, electrolyte tabletting, is filled for the first time
Discharge capacity 1920mAh/g.
Embodiment 4:
Graphene oxide sheet suspension preparation process is same as Example 1；
0.1g silicon nano (average grain diameter 50nm) is added to the above-mentioned graphene oxide suspension (lamella of 400mL
Size 10nm) in, so that it is uniformly dispersed in 250rpm mechanical stirring 60min, 1.2g reducing agent ascorbic acid is added, is warming up to 60
DEG C, 480min is stirred, is added and then is spray-dried, for inlet temperature at 200 DEG C, outlet temperature removes deionization at 110 DEG C
Water obtains the composite material of graphene and silicon；Then cooled to room temperature obtains carbon in lithium ion battery silicon composite cathode material
Material.As lithium ion battery negative material, it is packaged into button cell with positive electrode, diaphragm, electrolyte tabletting, is filled for the first time
Discharge capacity 1910mAh/g.
The present invention provides a kind of In-situ reaction preparation lithium ion battery carbon silicon anode material method thinking and method,
There are many method and the approach for implementing the technical solution, the above is only a preferred embodiment of the present invention, it is noted that
For those skilled in the art, without departing from the principle of the present invention, several change can also be made
Into and retouching, these modifications and embellishments should also be considered as the scope of protection of the present invention.Each component part being not known in the present embodiment
The available prior art is realized.
Claims (9)
1. a kind of method of In-situ reaction preparation lithium ion battery carbon silicon anode material, which comprises the steps of:
(1) prepared by graphene oxide: natural graphite powder being pre-processed using dilute hydrochloric acid, is then added to 0~3 DEG C of the concentrated sulfuric acid
In, NaNO is sequentially added under stirring3And KMnO4, and continue to be stirred to react 2~3h, until being moved into after solution is in blackish green
Continue to be stirred to react to solution in 30 DEG C of constant water bath box and becomes pink by blackish green；Then adds concentrated sulfuric acid solution and stir
1~2h is mixed, after solution is in bronzing, stirring 1h is further continued for and H is then added2O2Solution, until solution stirs again after becoming golden yellow
2h is mixed, is filtered while hot, product dilute hydrochloric acid solution and deionized water are washed repeatedly until sulfate radical-free ion in filtrate, warp
After drying to obtain the final product；
(2) graphene oxide sheet suspension prepare: the graphene oxide that step (1) is obtained in a solvent first ultrasonic treatment 1~
Then 2h turns/min with 5000-10000, be centrifuged 5-10min to remove unstripped substance, separation supernatant obtains oxidation stone
Black alkene piece suspension；
(3) prepared by carbon silicium cathode material: silicon nano is added in the graphene oxide sheet suspension that step (2) obtains,
And being sufficiently stirred makes it be uniformly dispersed, and reducing agent ascorbic acid is then added, is warming up to 50-80 DEG C, is stirred to react 60-
Then 600min is spray-dried to obtain the composite material of graphene and silicon, subsequent cooled to room temperature to obtain the final product.
2. the method for In-situ reaction preparation lithium ion battery carbon silicon anode material according to claim 1, which is characterized in that
In step (1), the natural graphite powder, the concentrated sulfuric acid, NaNO3And KMnO4Amount ratio be 2-6g:300-350ml:3.5-5g:
20-25g。
3. the method for In-situ reaction preparation lithium ion battery carbon silicon anode material according to claim 1, which is characterized in that
In step (1), the concentrated sulfuric acid solution concentration added is 98wt%, and dosage is 20-40ml/5g natural graphite powder；It is described
H2O2Solution concentration is 30wt%, and dosage is 10-40ml/5g natural graphite powder.
4. the method for In-situ reaction preparation lithium ion battery carbon silicon anode material according to claim 1, which is characterized in that
In step (2), the solvent is water or ethyl alcohol.
5. the method for In-situ reaction preparation lithium ion battery carbon silicon anode material according to claim 1, which is characterized in that
In step (2), in obtained graphene oxide sheet suspension, graphene oxide layer is having a size of 1-10nm, graphene oxide
Piece concentration is 0.1-2mg/mL.
6. the method for In-situ reaction preparation lithium ion battery carbon silicon anode material according to claim 1, which is characterized in that
In step (3), the grain diameter of the silicon nano is 1-50nm.
7. the method for In-situ reaction preparation lithium ion battery carbon silicon anode material according to claim 1, which is characterized in that
In step (3), the mass ratio of graphene oxide sheet and silicon nano is 1:0.2-1 in the graphene oxide sheet suspension:
2。
8. the method for In-situ reaction preparation lithium ion battery carbon silicon anode material according to claim 1, which is characterized in that
In step (3), the mass ratio of graphene oxide sheet and reducing agent ascorbic acid is 1 in the graphene oxide sheet suspension:
0.35-3.5。
9. the method for In-situ reaction preparation lithium ion battery carbon silicon anode material according to claim 1, which is characterized in that
In step (3), the inlet temperature of the spray drying is 180-220 DEG C, and outlet temperature is 90-130 DEG C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910231092.7A CN109950492A (en) | 2019-03-26 | 2019-03-26 | A kind of method of In-situ reaction preparation lithium ion battery carbon silicon anode material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910231092.7A CN109950492A (en) | 2019-03-26 | 2019-03-26 | A kind of method of In-situ reaction preparation lithium ion battery carbon silicon anode material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109950492A true CN109950492A (en) | 2019-06-28 |
Family
ID=67011736
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910231092.7A Pending CN109950492A (en) | 2019-03-26 | 2019-03-26 | A kind of method of In-situ reaction preparation lithium ion battery carbon silicon anode material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109950492A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111740084A (en) * | 2020-06-15 | 2020-10-02 | 石家庄尚太科技有限公司 | Sulfur-doped pre-lithiated silicon-carbon composite material and preparation method thereof |
| CN113415804A (en) * | 2021-07-29 | 2021-09-21 | 厦门海辰新能源科技有限公司 | Carbon-silicon three-dimensional structure composite material and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101478043A (en) * | 2009-01-08 | 2009-07-08 | 上海交通大学 | Negative pole material for lithium ionic cell and preparation process thereof |
| CN101593827A (en) * | 2009-07-10 | 2009-12-02 | 浙江大学 | Silicon/negative pole made of silicon/graphite nanosheet composite material of lithium ion battery and preparation method thereof |
| CN104649255A (en) * | 2014-12-11 | 2015-05-27 | 宋鹏 | Method for preparing graphene through ball mill aided oxidation and reduction |
| CN105304884A (en) * | 2015-05-18 | 2016-02-03 | 深圳市国创新能源研究院 | Graphene-based silicon-carbon composite anode material and preparation method thereof |
| CN106032585A (en) * | 2015-03-13 | 2016-10-19 | 中国科学院上海应用物理研究所 | Graphene-inorganic nanometer particle composite fiber and preparing method thereof |
-
2019
- 2019-03-26 CN CN201910231092.7A patent/CN109950492A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101478043A (en) * | 2009-01-08 | 2009-07-08 | 上海交通大学 | Negative pole material for lithium ionic cell and preparation process thereof |
| CN101593827A (en) * | 2009-07-10 | 2009-12-02 | 浙江大学 | Silicon/negative pole made of silicon/graphite nanosheet composite material of lithium ion battery and preparation method thereof |
| CN104649255A (en) * | 2014-12-11 | 2015-05-27 | 宋鹏 | Method for preparing graphene through ball mill aided oxidation and reduction |
| CN106032585A (en) * | 2015-03-13 | 2016-10-19 | 中国科学院上海应用物理研究所 | Graphene-inorganic nanometer particle composite fiber and preparing method thereof |
| CN105304884A (en) * | 2015-05-18 | 2016-02-03 | 深圳市国创新能源研究院 | Graphene-based silicon-carbon composite anode material and preparation method thereof |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111740084A (en) * | 2020-06-15 | 2020-10-02 | 石家庄尚太科技有限公司 | Sulfur-doped pre-lithiated silicon-carbon composite material and preparation method thereof |
| CN111740084B (en) * | 2020-06-15 | 2021-11-23 | 石家庄尚太科技股份有限公司 | Sulfur-doped pre-lithiated silicon-carbon composite material and preparation method thereof |
| CN113415804A (en) * | 2021-07-29 | 2021-09-21 | 厦门海辰新能源科技有限公司 | Carbon-silicon three-dimensional structure composite material and preparation method thereof |
| US11817574B2 (en) | 2021-07-29 | 2023-11-14 | Xiamen Hithium Energy Storage Technology Co., Ltd. | Carbon-silicon three-dimensional structural composite material and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Yang et al. | Mesoporous CoSe2 nanoclusters threaded with nitrogen-doped carbon nanotubes for high-performance sodium-ion battery anodes | |
| Yi et al. | A flexible micro/nanostructured Si microsphere cross-linked by highly-elastic carbon nanotubes toward enhanced lithium ion battery anodes | |
| Cheng et al. | CeO2 decorated graphene as separator modification material for capture and boost conversion of polysulfide in lithium-sulfur batteries | |
| Hao et al. | Hierarchical three-dimensional Fe3O4@ porous carbon matrix/graphene anodes for high performance lithium ion batteries | |
| Yuan et al. | Polysulfides anchoring and enhanced electrochemical kinetics of 3D flower-like FeS/carbon assembly materials for lithium-sulfur battery | |
| Chu et al. | NiO nanocrystals encapsulated into a nitrogen-doped porous carbon matrix as highly stable Li-ion battery anodes | |
| Qiu et al. | Biomass-derived, 3D interconnected N-doped carbon foam as a host matrix for Li/Na/K-selenium batteries | |
| Ye et al. | Facile preparation of graphene nanosheets encapsulated Fe3O4 octahedra composite and its high lithium storage performances | |
| Xu et al. | NiO/CNTs derived from metal-organic frameworks as superior anode material for lithium-ion batteries | |
| CN105826527A (en) | Porous silicon-carbon composite material and preparation method and application thereof | |
| Ye et al. | Fe3Se4 nanoparticles confined in hollow carbon nanocages for high-performance sodium-ion batteries | |
| Jiang et al. | A novel CoO hierarchical morphologies on carbon nanofiber for improved reversibility as binder-free anodes in lithium/sodium ion batteries | |
| CN106206059A (en) | NiCo2s4the preparation method and application of/graphite felt combination electrode material | |
| Zhang et al. | Functionalized hierarchical porous carbon with sulfur/nitrogen/oxygen tri-doped as high quality sulfur hosts for lithium-sulfur batteries | |
| CN109411713A (en) | The machinery of the modified composite material of siliceous substrates material is total to method for coating, modified composite material and lithium ion battery | |
| CN109244378A (en) | Preparation method of porous nano silicon-carbon composite material | |
| Wu et al. | Encapsulation of sulfur cathodes by sericin-derived carbon/Co3O4 hollow microspheres for the long-term cyclability of lithium-sulfur batteries | |
| Li et al. | Architecture and performance of Si/C microspheres assembled by nano-Si via electro-spray technology as stability-enhanced anodes for lithium-ion batteries | |
| Liu et al. | 3D nanoflower-like MoS2 grown on wheat straw cellulose carbon for lithium-ion battery anode material | |
| CN112357956B (en) | Carbon/titanium dioxide coated tin oxide nanoparticle/carbon assembled mesoporous sphere material and preparation and application thereof | |
| Ren et al. | Preparation of zinc sulfide@ reduced graphene oxide nanocomposites with enhanced energy storage performance | |
| Liu et al. | Multiple roles of titanium carbide in performance boosting: Mediator, anchor and electrocatalyst for polysulfides redox regulation | |
| Yang et al. | A facile synthetic strategy of free-standing holey graphene paper as sulfur host for high-performance flexible lithium sulfur batteries | |
| CN114242961B (en) | Graphene/silicon oxide coated nano-silicon composite material and preparation method and application thereof | |
| CN109950492A (en) | A kind of method of In-situ reaction preparation lithium ion battery carbon silicon anode material |
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 | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20190628 |