CN107146887A - Carbon nanometer three-dimensional structure composite for negative electrode of lithium ion battery and preparation method thereof - Google Patents
Carbon nanometer three-dimensional structure composite for negative electrode of lithium ion battery and preparation method thereof Download PDFInfo
- Publication number
- CN107146887A CN107146887A CN201710233548.4A CN201710233548A CN107146887A CN 107146887 A CN107146887 A CN 107146887A CN 201710233548 A CN201710233548 A CN 201710233548A CN 107146887 A CN107146887 A CN 107146887A
- Authority
- CN
- China
- Prior art keywords
- dimensional structure
- lithium ion
- ion battery
- carbon nanometer
- negative electrode
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- 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 relates to a kind of for carbon nanometer three-dimensional structure composite of negative electrode of lithium ion battery and preparation method thereof, the composite is the porous three-dimensional structure being made up of graphene, CNT or their mixture.It is in the aqueous solution of carbon material, to add reducing agent reduction that it, which is prepared, or adds polyvinyl alcohol using high-temperature calcination reduction, obtains carbon nanometer three-dimensional structure composite.Compared with prior art, three-dimensional structure produced by the present invention can be directly used for making lithium ion battery, show preferably charge-discharge performance；Prepare simply, can be formed directly in the macro-scale material with certain manipulation strength, and can directly cut application, advantageously reduce the weight of lithium ion battery, improve the service efficiency of battery unit mass；Simplify the technological process of battery assembling.The lithium ion that the three-dimensional structure of the present invention makes still can reach more than 99.9% efficiency after 400 circulations of discharge and recharge.
Description
Technical field
It is three-dimensional more particularly to a kind of carbon nanometer for negative electrode of lithium ion battery the invention belongs to carbon nanomaterial field
Structural composite material and preparation method thereof.
Background technology
The material for the two-dimension periodic honeycomb lattice structure that graphene is made up of hexatomic ring, graphene three-dimensional structure is one
Kind there is super highly porous solid, be also the minimum solid of world upper density, most light graphene three-dimensional structure is close at present
Degree is only 0.16mg/cm3, while graphene aerogel also has up to 2630m2.g-1Specific surface area, 5000W.m-1.K-1's
Carrier mobility speed.Meanwhile, the utilization of graphene three-dimensional structure is solved the premium properties of graphene from microcosmic well
Field extends to macroscopic arts.
Since lithium ion battery was commercialized before more than 20 years, portable type electronic product has been had been widely used for.Electronic vapour
The fields such as car.The negative material of traditional lithium ion battery is mainly graphite, still, development and science skill with modern society
The progress of art, using negative material of the graphite as lithium ion battery, its theoretical circulation capacity and energy density can not expire
Use requirement of the sufficient people to battery.There is graphene individual layer two-dimensional structure to be easier to realize the transmission of lithium ion in theory,
So as to improve the performance of lithium ion.
Patent No. CN103985847A【Zhang Lifeng, Zhang Jinzhen, Liu Yi, Guo Shouwu, a kind of lithium ion battery with zinc oxide/
The preparation method of graphene composite material】Using graphene as negative material lithium ion battery assembled battery technique stream
All it is to use to pulverize graphene three-dimensional structure last to add various conductive agents and binder making into conduction electrocoagulation in terms of journey
Slurry, then by conduction electrocoagulation slurry be applied to above collector after using vacuum high-temperature dry, be finally only and be assembled into battery.Such side
Not only technological process is tediously long for method, is not suitable for industrialized production；Meanwhile, three-dimensional structure is ground to form to the powder of two dimension, it is impossible to
Aeroge three-dimensional structure is given full play to as the characteristic of a three-dimensional conductive network.
Patent No. CN104362304A【It is prepared by Li Hongliang, Jing Laixing, Fu Aiping, Wang Yiqian, a kind of hot step of high-temperature solvent
Fe3O4aThe method of/graphene lithium ion battery composite negative pole material】Fe is prepared using the hot step of high-temperature solvent3O4/ graphene lithium
Ion battery composite negative pole material, is carried out, the Fe of generation under high temperature, high pressure solvent thermal environment3O4Direct combination is in graphene
Surface, without further calcining, so as to obtain that crystal formation is complete and the good composite of chemical property.But, in assembling
During into button cell, it is necessary to by the Fe of preparation3O4/ graphene composite material is pulverized last with acetylene black, Kynoar etc.
Additive is mixed according to different ratios in 1-METHYLPYRROLIDONE, and even application is on copper foil.10 are dried in vacuo at 120 DEG C
It is punched out after hour, has finally just carried out the assembling of battery, so not only caused the technological process of composition battery to become tediously long,
The need for being not suitable for socialization production, while also destroying the three-dimensional structure of graphene, it is impossible to give full play to graphene three-dimensional knot
Structure is as three-dimensional conductive network and with good anti-compression properties.
Patent No. CN104271497A【Sun Peiyu, Liu Gangqiao, Wu Zhenqi, Wu Gang, the beautiful flourish youth of wood, Kubo Tian Taisheng, stone
The lithium ion battery battery of black alkene powder, the method for preparing graphene powder and graphene-containing powder】Be prepared for it is highly conductive,
Highly dispersible graphene powder and the electricity by conductive, the highly dispersible graphene powder for lithium ion battery
Pole.But, carbon black is with the addition of when applying to lithium ion battery as conductive additive at the same also added metal dust etc. its
His conductive additive, it reduce graphene purity in battery, reduces the service efficiency of graphene, increases battery unit matter
The service efficiency of amount；By graphene grind into powder, graphene three-dimensional structure can not be given full play to conductive as space three-dimensional
The advantage of network.
The content of the invention
It is an object of the present invention to overcome the above-mentioned drawbacks of the prior art and provide one kind is used for lithium-ion electric
Carbon nanometer three-dimensional structure composite of pond negative pole and preparation method thereof.
The purpose of the present invention can be achieved through the following technical solutions：A kind of carbon nanometer for negative electrode of lithium ion battery
Three-dimensional structure composite, it is characterised in that the composite is made up of graphene, CNT or their mixture
Porous three-dimensional structure.
Described composite is the wafer architecture that thickness is 1~2mm.
A kind of preparation method of carbon nanometer three-dimensional structure composite for negative electrode of lithium ion battery, it is characterised in that
This method comprises the following steps：In the aqueous solution of carbon material, reducing agent reduction is added, or adds polyvinyl alcohol and is forged using high temperature
Reduction is burnt, carbon nanometer three-dimensional structure composite is obtained.
Described carbon material be graphene oxide water solution or CNT, or both mixture.
Described graphene oxide water solution is to use Hummers methods to prepare oxidation of the solubility for 2~8mg/ml
Graphene aqueous solution.
Described CNT is a diameter of 10~20nm, and length is 1~5 μm of oxide/carbon nanometer tube, is by by city
CNT is sold using the concentrated sulfuric acid and concentrated nitric acid by 4:1 ratio is washed till in suction filtration molten with deionized water after aoxidizing 7~8 hours
Liquid neutrality is obtained.
Described reducing agent includes：Ascorbic acid, hydrazine hydrate, sodium sulfite, ammoniacal liquor or hydrogen iodide.
Described carbon nanometer three-dimensional structure composite diameter is used for negative electrode of lithium ion battery, it is not necessary to by grinding, match somebody with somebody
Slurrying material, is applied on collector, the step such as vacuum drying, it is not necessary to add the materials such as conductive black, adhesive.
The specific method that carbon nanometer three-dimensional structure composite is made in above-mentioned reducing agent reduction or high-temperature calcination is as follows：
Use the preparation method for the graphene three-dimensional structure that reducing agent reduces for：Prepared using Hummers methods molten
The graphene oxide water solution (i.e. the GO aqueous solution) for 2~8mg/ml is spent, reducing agent, graphene oxide are added in the GO aqueous solution
Mass ratio with reducing agent is 16~48:50~5000,5~10min is stirred, resulting solution is instilled in the mould of cylinder, will
Mould is sealed and in reductase 12~5 hour in 70~80 DEG C, and graphene hydrogel is made, hydrogel is placed in 6 in deionized water~
The step is repeated 2~4 times within 12 hours, is freeze-dried 24~48 hours, that is, is prepared the stone for the wafer architecture that thickness is about 1~2mm
Black alkene three-dimensional structure.
Use low-temperature reduction graphene/carbon nano-tube three-dimensional structure preparation method for：Oxygen is added in the GO aqueous solution
Change CNT, then 60~120min of ultrasound, be subsequently agitated for 60~120min, add reducing agent, graphene oxide, carbonoxide nanometer
The mass ratio of pipe and reducing agent is 16~48：10~20：50~500,5~30min is stirred, solution is instilled to the mould of cylinder
In, mould is sealed and in reductase 12~5 hour in 70~80 DEG C, obtain graphene/carbon nano-tube hydrogel, hydrogel is put
24~48 hours in deionized water, it is freeze-dried 24~48 hours, that is, prepares the stone for the wafer architecture that thickness is about 1~2mm
Black alkene/CNT three-dimensional structure.
Use the preparation method for the graphene three-dimensional structure that high-temperature calcination reduces for：Polyethylene is added in the GO aqueous solution
The mass ratio of alcohol, graphene oxide and polyvinyl alcohol is 16~48：40~60,30~60min is stirred, resulting solution is instilled and justified
In the mould of cylindricality, freezed 2~3 hours in -40~-70 DEG C, then vacuumize and dry 24~48 hours, after the completion of drying,
Three-dimensional structure is tentatively pyrolyzed at 550~650 DEG C, then carrying out second at 1000~1100 DEG C is pyrolyzed, that is, prepares thickness
Degree is about the graphene three-dimensional structure of 1~2mm wafer architecture.
Use the preparation method for the graphene/carbon nano-tube three-dimensional structure that high-temperature calcination reduces for：In 4~6ml GO water
10~20mg oxide/carbon nanometer tubes are added in solution, polyvinyl alcohol, graphene oxide, oxide/carbon nanometer tube and poly- second is subsequently added
The mass ratio of enol is 16~48：10~20：40~60,30~60min is stirred, resulting solution is instilled to the mould of cylinder
In, freezed 2~3 hours in -40~-70 DEG C, then vacuumize and dry 24~48 hours, after the completion of drying, to three-dimensional structure
Tentatively be pyrolyzed at 550~650 DEG C, then carrying out second at 1000~1100 DEG C is pyrolyzed, that is, prepare thickness be about 1~
The graphene/carbon nano-tube three-dimensional structure of 2mm wafer architecture.
Compared with prior art, material of the present invention is directly constituted three-dimensional structure and led by highly conductive CNT, graphene
Electric network, thus preferably charge-discharge performance is shown, it still can reach more than 99.9% after 400 circulations of discharge and recharge
Efficiency；Because graphene three-dimensional structure is directly used in the electrode material of lithium ion battery by the present invention, and it need not again add and appoint
What conductive materials and binding agent, improve service efficiency of the graphene three-dimensional structure in battery electrode；Simultaneously can be with
The weight of battery is reduced, the service efficiency of battery Unit Weight is improved.In terms of assembled battery technological process, different from traditional
Battery packaging technology need by three-dimensional structure pulverize it is last addition conductive materials and coagulating agent be configured to conduction electrocoagulation slurry, then
Conduction electrocoagulation slurry uniformly is applied to above collector, and the environment of 100 DEG C of vacuum is placed in by the collector that conduction electrocoagulation starches has been smeared
In be dried, finally will just dry the collector that completes and apply to the assembling of battery.The present invention is directly three-dimensional using graphene
Structure, three-dimensional structure has been made 1~2mm is high, and radius is 6~8mm cylindrical structure, and is directly used in the assembling of battery, makes
It is standby simple, the macro-scale material with certain manipulation strength is can be formed directly in, and application can be directly cut, it is not required to carry out routine
Electric conductivity, binding agent mixing, drying and other steps in lithium-ion negative pole preparation.Graphene three-dimensional knot so can be both given full play to
Structure has the advantage of space three-dimensional high conductivity；The preferable elasticity that can also have using three-dimensional structure, it is ensured that each in battery
The abundant contact of individual component；Finally, the composition flow for simplifying battery of high degree so that the assembling of battery is more suitable for industry
Metaplasia is produced.
Embodiment
With reference to specific embodiment, the present invention is described in detail.
The CNT that the present invention is used is a diameter of 10~20nm, and length is 1~5 μm of oxide/carbon nanometer tube, is logical
Cross commercially available CNT using the concentrated sulfuric acid and concentrated nitric acid by 4:1 ratio uses deionized water in suction filtration after aoxidizing 7~8 hours
Solution neutrality is washed till to obtain.
The carbon material three-dimensional structure composite that the inventive method is obtained is directly used in the assembling of lithium ion battery, and carries out
Charge-discharge test.
Embodiment 1
50mg ascorbic acid is added in the 4ml GO aqueous solution, 5min is stirred, solution is instilled to the mould of cylinder
In, mould is sealed and in being reduced 4 hours in 70 DEG C, graphene hydrogel is made, it is small that hydrogel is placed in deionized water into 24
When, it is freeze-dried 24 hours, that is, prepares the graphene three-dimensional structure for the wafer architecture that thickness is about 1~2mm.
The three-dimensional structure prepared is directly used in the assembling of lithium ion battery and tested.It is to use in this example
CR2025 type button cells, cobalt acid lithium (LiCoO2) as to electrode, barrier film is the type micro-pore septums of Celgard 2325, electrolyte
For 1M LiPF6Ethylene carbonate (EC) and dimethyl carbonate (DMC) volume ratio be 1:1 solution.In 200mAh/g charge and discharge
Under the conditions of electricity, and charge-discharge test is carried out, more than 99.9% efficiency still can be reached after 400 circulations of discharge and recharge.
Embodiment 2
Use the preparation method for the graphene/carbon nano-tube three-dimensional structure that reducing agent reduces for：In the 4ml GO aqueous solution
10mg oxidation CNT are added, then ultrasound 60min, is subsequently agitated for 60min, adds 50mg ascorbic acid, 5min is stirred, by solution
In the mould for instilling cylinder, mould is sealed and in being reduced 4 hours in 70 DEG C, graphene/carbon nano-tube hydrogel is obtained, will
Hydrogel is placed in deionized water 24 hours, is freeze-dried 24 hours, that is, is prepared the stone for the wafer architecture that thickness is about 1~2mm
Black alkene/CNT three-dimensional structure.
The three-dimensional structure prepared is directly used in the assembling of lithium ion battery and tested.It is to use in this example
CR2025 type button cells, cobalt acid lithium (LiCoO2) as to electrode, barrier film is the type micro-pore septums of Celgard 2325, electrolyte
For 1M LiPF6Ethylene carbonate (EC) and dimethyl carbonate (DMC) volume ratio be 1:1 solution.In 200mAh/g charge and discharge
Under the conditions of electricity, and charge-discharge test is carried out, more than 99.9% efficiency still can be reached after 400 circulations of discharge and recharge.It is real
Apply example 3
Use the preparation method for the graphene three-dimensional structure that high-temperature calcination reduces for：Added in the 4ml GO aqueous solution
40mg polyvinyl alcohol, stirs 30min, in the mould that solution is instilled to cylinder, freezes 2 hours, then vacuumizes in -60 DEG C
Dry 24 hours.After the completion of drying, aeroge is tentatively pyrolyzed at 550 DEG C, then carrying out second at 1000 DEG C is pyrolyzed,
Prepare the graphene aerogel for the wafer architecture that thickness is about 1~2mm.
The three-dimensional structure prepared is directly used in the assembling of lithium ion battery and tested.It is to use in this example
CR2025 type button cells, cobalt acid lithium (LiCoO2) as to electrode, barrier film is the type micro-pore septums of Celgard 2325, electrolyte
For 1M LiPF6Ethylene carbonate (EC) and dimethyl carbonate (DMC) volume ratio be 1:1 solution.In 200mAh/g charge and discharge
Under the conditions of electricity, and charge-discharge test is carried out, more than 99.9% efficiency still can be reached after 400 circulations of discharge and recharge.It is real
Apply example 4
Use the preparation method for the graphene/carbon nano-tube aeroge that high-temperature calcination reduces for：In the 4ml GO aqueous solution
10~20mg oxide/carbon nanometer tubes are added, 40mg polyvinyl alcohol is subsequently added, 30min is stirred, solution is instilled to the mould of cylinder
In tool, freezed 2 hours in -60 DEG C, then vacuumize and dry 24 hours.After the completion of drying, aeroge is carried out just at 550 DEG C
Step pyrolysis, then carries out second at 1000 DEG C and is pyrolyzed, that is, the graphene/carbon for preparing the wafer architecture that thickness is about 1~2mm is received
Mitron aeroge.
The three-dimensional structure prepared is directly used in the assembling of lithium ion battery and tested.It is to use in this example
CR2025 type button cells, cobalt acid lithium (LiCoO2) as to electrode, barrier film is the type micro-pore septums of Celgard 2325, electrolyte
For 1M LiPF6Ethylene carbonate (EC) and dimethyl carbonate (DMC) volume ratio be 1:1 solution.In 200mAh/g charge and discharge
Under the conditions of electricity, and charge-discharge test is carried out, more than 99.9% efficiency still can be reached after 400 circulations of discharge and recharge.It is real
Apply example 5
5000mg ascorbic acid is added in the 6ml GO aqueous solution, 10min is stirred, solution is instilled to the mould of cylinder
In tool, mould is sealed and in being reduced 5 hours in 80 DEG C, graphene hydrogel is made, it is small that hydrogel is placed in deionized water into 8
When, it is freeze-dried 48 hours, that is, prepares the graphene three-dimensional structure for the wafer architecture that thickness is about 1~2mm.
The three-dimensional structure prepared is directly used in the assembling of lithium ion battery and tested.It is to use in this example
CR2025 type button cells, cobalt acid lithium (LiCoO2) is as to electrode, and barrier film is the type micro-pore septums of Celgard 2325, electrolyte
It is 1 for 1M LiPF6 ethylene carbonate (EC) and dimethyl carbonate (DMC) volume ratio:1 solution.In 200mAh/g charge and discharge
Under the conditions of electricity, and charge-discharge test is carried out, more than 99.9% efficiency still can be reached after 400 circulations of discharge and recharge.It is real
Apply example 6
The preparation method of the described graphene/carbon nano-tube three-dimensional structure for using reducing agent to reduce for：In 6ml GO water
20mg oxidation CNT are added in solution, then ultrasound 120min, is subsequently agitated for 120min, add 500mg ascorbic acid, stirring
In 10min, the mould that solution is instilled to cylinder, mould is sealed and in being reduced 5 hours in 80 DEG C, obtains graphene/carbon and receives
Mitron hydrogel, hydrogel is placed in deionized water 48 hours, is freeze-dried 48 hours, that is, it is about 1~2mm's to prepare thickness
The graphene/carbon nano-tube three-dimensional structure of wafer architecture.
The three-dimensional structure prepared is directly used in the assembling of lithium ion battery and tested.It is to use in this example
CR2025 type button cells, cobalt acid lithium (LiCoO2) is as to electrode, and barrier film is the type micro-pore septums of Celgard 2325, electrolyte
It is 1 for 1M LiPF6 ethylene carbonate (EC) and dimethyl carbonate (DMC) volume ratio:1 solution.In 200mAh/g charge and discharge
Under the conditions of electricity, and charge-discharge test is carried out, more than 99.9% efficiency still can be reached after 400 circulations of discharge and recharge.
Embodiment 7
Use the preparation method for the graphene three-dimensional structure that high-temperature calcination reduces for：Added in the 6ml GO aqueous solution
60mg polyvinyl alcohol, stirs 60min, and solution is instilled in 8 cylindrical moulds, freezes 3 hours, then takes out in -70 DEG C
Vacuum drying 48 hours.After the completion of drying, three-dimensional structure is tentatively pyrolyzed at 650 DEG C, then second is carried out at 1100 DEG C
Secondary pyrolysis, that is, prepare the graphene three-dimensional structure for the wafer architecture that thickness is about 1~2mm.
The three-dimensional structure prepared is directly used in the assembling of lithium ion battery and tested.It is to use in this example
CR2025 type button cells, cobalt acid lithium (LiCoO2) is as to electrode, and barrier film is the type micro-pore septums of Celgard 2325, electrolyte
It is 1 for 1M LiPF6 ethylene carbonate (EC) and dimethyl carbonate (DMC) volume ratio:1 solution.In 200mAh/g charge and discharge
Under the conditions of electricity, and charge-discharge test is carried out, more than 99.9% efficiency still can be reached after 400 circulations of discharge and recharge.
Embodiment 8
Use the preparation method for the graphene/carbon nano-tube three-dimensional structure that high-temperature calcination reduces for：In the 6ml GO aqueous solution
Middle addition 20mg oxide/carbon nanometer tubes, are subsequently added 60mg polyvinyl alcohol, stir 60min, and solution is instilled to the mould of cylinder
In, freezed 3 hours in -70 DEG C, then vacuumize and dry 48 hours.After the completion of drying, three-dimensional structure is carried out just at 650 DEG C
Step pyrolysis, then carries out second at 1100 DEG C and is pyrolyzed, that is, the graphene/carbon for preparing the wafer architecture that thickness is about 1~2mm is received
Mitron three-dimensional structure.
The three-dimensional structure prepared is directly used in the assembling of lithium ion battery and tested.It is to use in this example
CR2025 type button cells, cobalt acid lithium (LiCoO2) is as to electrode, and barrier film is the type micro-pore septums of Celgard 2325, electrolyte
It is 1 for 1M LiPF6 ethylene carbonate (EC) and dimethyl carbonate (DMC) volume ratio:1 solution.In 200mAh/g charge and discharge
Under the conditions of electricity, and charge-discharge test is carried out, more than 99.9% efficiency still can be reached after 400 circulations of discharge and recharge.
Claims (8)
1. a kind of carbon nanometer three-dimensional structure composite for negative electrode of lithium ion battery, it is characterised in that the composite is
The porous three-dimensional structure being made up of graphene, CNT or their mixture.
2. a kind of carbon nanometer three-dimensional structure composite for negative electrode of lithium ion battery according to claim 1, it is special
Levy and be, described composite is the wafer architecture that thickness is 1~2mm.
3. a kind of system of the carbon nanometer three-dimensional structure composite as claimed in claim 1 or 2 for negative electrode of lithium ion battery
Preparation Method, it is characterised in that this method comprises the following steps：In the aqueous solution of carbon material, reducing agent reduction is added, or add
Polyvinyl alcohol is reduced using high-temperature calcination, obtains carbon nanometer three-dimensional structure composite.
4. a kind of preparation of carbon nanometer three-dimensional structure composite for negative electrode of lithium ion battery according to claim 3
Method, it is characterised in that described carbon material be graphene oxide water solution or CNT, or both mixture.
5. a kind of preparation of carbon nanometer three-dimensional structure composite for negative electrode of lithium ion battery according to claim 4
Method, it is characterised in that described graphene oxide water solution is to use Hummers methods to prepare solubility for 2~8mg/
Ml graphene oxide water solution.
6. a kind of preparation of carbon nanometer three-dimensional structure composite for negative electrode of lithium ion battery according to claim 4
Method, it is characterised in that described CNT is a diameter of 10~20nm, length is 1~5 μm of oxide/carbon nanometer tube, is
By the way that commercially available CNT is pressed into 4 using the concentrated sulfuric acid and concentrated nitric acid:1 ratio heated oxide is existed after 7~8 hours with deionized water
Solution neutrality is washed till in suction filtration to obtain.
7. a kind of preparation of carbon nanometer three-dimensional structure composite for negative electrode of lithium ion battery according to claim 3
Method, it is characterised in that described reducing agent includes：Ascorbic acid, hydrazine hydrate, sodium sulfite, ammoniacal liquor or hydrogen iodide.
8. a kind of preparation of carbon nanometer three-dimensional structure composite for negative electrode of lithium ion battery according to claim 3
Method, it is characterised in that described carbon nanometer three-dimensional structure composite diameter is used for negative electrode of lithium ion battery.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710233548.4A CN107146887A (en) | 2017-04-11 | 2017-04-11 | Carbon nanometer three-dimensional structure composite for negative electrode of lithium ion battery and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710233548.4A CN107146887A (en) | 2017-04-11 | 2017-04-11 | Carbon nanometer three-dimensional structure composite for negative electrode of lithium ion battery and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN107146887A true CN107146887A (en) | 2017-09-08 |
Family
ID=59774646
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710233548.4A Pending CN107146887A (en) | 2017-04-11 | 2017-04-11 | Carbon nanometer three-dimensional structure composite for negative electrode of lithium ion battery and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107146887A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107706391A (en) * | 2017-10-16 | 2018-02-16 | 常州大学 | A kind of C-base composte material of low-temperature lithium ion battery and preparation method thereof |
| CN109148870A (en) * | 2018-09-29 | 2019-01-04 | 上海理工大学 | A kind of preparation method of high performance carbon phosphorus composite negative pole material |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101993056A (en) * | 2010-12-01 | 2011-03-30 | 天津大学 | Graphene-based porous macroscopic carbon material and preparation method thereof |
| CN103384007A (en) * | 2013-07-23 | 2013-11-06 | 深圳清华大学研究院 | Carbon nano tube/graphene composite negative pole material, preparation method thereof and lithium battery |
| CN105161736A (en) * | 2015-08-19 | 2015-12-16 | 哈尔滨工业大学 | Miniature direct methanol fuel cell membrane electrode and preparation method thereof |
| CN105948029A (en) * | 2016-05-09 | 2016-09-21 | 东华大学 | Graphene roll/carbon nanotube composite aerogel material, preparation and application thereof |
-
2017
- 2017-04-11 CN CN201710233548.4A patent/CN107146887A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101993056A (en) * | 2010-12-01 | 2011-03-30 | 天津大学 | Graphene-based porous macroscopic carbon material and preparation method thereof |
| CN103384007A (en) * | 2013-07-23 | 2013-11-06 | 深圳清华大学研究院 | Carbon nano tube/graphene composite negative pole material, preparation method thereof and lithium battery |
| CN105161736A (en) * | 2015-08-19 | 2015-12-16 | 哈尔滨工业大学 | Miniature direct methanol fuel cell membrane electrode and preparation method thereof |
| CN105948029A (en) * | 2016-05-09 | 2016-09-21 | 东华大学 | Graphene roll/carbon nanotube composite aerogel material, preparation and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| YUHAI HU等: ""Free-standing graphene-carbon nanotube hybrid papers used as current collector and binder free anodes for lithium ion batteries"", 《JOURNAL OF POWER SOURCES》 * |
| 刘学发: ""气凝胶及其复合材料的研究"", 《中国优秀硕士学位论文全文数据库（电子期刊） 工程科技I辑》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107706391A (en) * | 2017-10-16 | 2018-02-16 | 常州大学 | A kind of C-base composte material of low-temperature lithium ion battery and preparation method thereof |
| CN107706391B (en) * | 2017-10-16 | 2020-06-02 | 常州大学 | Carbon-based composite material of low-temperature lithium ion battery and preparation method thereof |
| CN109148870A (en) * | 2018-09-29 | 2019-01-04 | 上海理工大学 | A kind of preparation method of high performance carbon phosphorus composite negative pole material |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102810664B (en) | The preparation method of dispersed nano olivine-type manganese based phosphates positive electrode and lithium rechargeable battery thereof | |
| CN101800311B (en) | Method for preparing lithium iron phosphate with high rate discharge by using ultrasonic coprecipitation | |
| CN104934579B (en) | A kind of porous graphite doping and the preparation method of carbon coating graphite cathode material | |
| CN105449209B (en) | A kind of lithium sulfur battery anode material of richness nitrogen eggshell type, preparation method and applications | |
| CN104659366A (en) | Preparation method of anode material for power lithium ion battery | |
| CN102867940B (en) | Process for preparing lithium sulfur battery modified anode | |
| CN103427069B (en) | A kind of composite cathode material for lithium ion cell and preparation thereof | |
| CN104085877A (en) | Porous carbon electrode material based on chitosan and derivative of chitosan thereof as well as preparation method and application of porous carbon electrode material | |
| CN103165894B (en) | Graphene-hydroxyl lithium composite and its preparation method and application | |
| CN104934603A (en) | Preparation method of graphene-dopedand carbon-coated modified graphite anode material | |
| CN106328913A (en) | Surface modification method for silicon negative electrode material of lithium ion battery, silicon negative electrode material and application | |
| CN108630889A (en) | A kind of lithium-sulfur cell and its anode and preparation method using nitride/graphene as interlayer | |
| CN105206809A (en) | C3N4-carbon-coated lithium iron phosphate composite anode material and preparation method thereof | |
| CN103346302A (en) | Lithium battery silicon-carbon nanotube composite cathode material as well as preparation method and application thereof | |
| CN109950487A (en) | A kind of lithium sulfur battery anode material and preparation method thereof | |
| CN108134087A (en) | Negative material and preparation method thereof used in a kind of lithium-ion-power cell | |
| CN102683662B (en) | Lithium-ion battery and manufacturing method thereof | |
| CN114583093A (en) | Preparation method and application of high-energy-density hard carbon composite negative electrode material | |
| CN114613974A (en) | Long-life quick-charging type lithium ion battery cathode material and preparation method thereof | |
| CN107146887A (en) | Carbon nanometer three-dimensional structure composite for negative electrode of lithium ion battery and preparation method thereof | |
| CN106745284A (en) | A kind of preparation method of manganese dioxide nano pipe and its applied in terms of lithium battery | |
| CN104183836A (en) | Positive electrode composite material for lithium sulfur battery | |
| CN104241606B (en) | Preparation method of lithium iron phosphate positive plate with high rate and superior low-temperature performance | |
| CN103268939A (en) | Preparation method of lithium ferrous silicate anode composite material | |
| CN106532056A (en) | Anti-expansion additive for lithium titanate electrode material and preparation method for anti-expansion additive |
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: 20170908 |