CN104045080A - Activated graphene sheet and preparation method thereof - Google Patents
Activated graphene sheet and preparation method thereof Download PDFInfo
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- CN104045080A CN104045080A CN201410295938.0A CN201410295938A CN104045080A CN 104045080 A CN104045080 A CN 104045080A CN 201410295938 A CN201410295938 A CN 201410295938A CN 104045080 A CN104045080 A CN 104045080A
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- graphene film
- activation
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- potassium permanganate
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Abstract
The invention provides an activated graphene sheet and a preparation method thereof. The preparation method of the activated graphene sheet comprises the steps of adding sulfuric acid, nitric acid and potassium permanganate to carry out intercalation treatment on a graphene sheet serving as a raw material and then carrying out KOH activation process. The activated graphene sheet disclosed by the invention has the advantages of good conductivity, large specific surface area, high mesopore content, less impurities, low production cost, low equipment investment, simple operation, excellent electrochemical properties and good physical and chemical stabilities and can be put into industrialization easily.
Description
Technical field
The invention belongs to high-performance carbon element material field, be specifically related to a kind of activation graphene film and preparation method thereof.
Background technology
2004, after obtaining high-quality graphene film by the professor An Deliehaimu of Univ Manchester UK and Constantine Nuo Woxiaoluofu by simple adhesive tape stickily tear method, because Graphene is with extremely superior physicals, the characteristics such as the thermal conductivity of unusual quantum hall effect, superelevation, good chemical property have a wide range of applications in the exploitation of the novel material such as semi-conductor, new forms of energy and device.Graphene is a kind of two-dimensional material, and specific surface area reaches 2600m in theory
2/ g, large specific surface area and the electroconductibility of superelevation, make Graphene become the popular research directions such as various electrode of electrochemical device materials.But in reality, due to the large pi-conjugated architectural characteristic of two dimension of Graphene, in preparation process, easily reunite, occur between layers stacking, this by greatly reduce Graphene high-specific surface area at new device as making full use of between ultracapacitor, thereby reduce the performance of material.The method that the utilization of raising Graphene specific surface area is applied on each device also is constantly being excavated out, how to utilize to greatest extent the specific surface of Graphene and electroconductibility to remain a challenge.
Activation is a kind of conventional method of preparing porous carbon material.Can improve specific surface area and the capacitive property of Carbon Materials by activation.Chemical activation is the activation method of relatively commonly using, and by increasing vesicular structure at graphene film, reaches the effect that increases specific surface area.The shape in hole and size distribution determining graphene film at each device as the performance of electrode material for super capacitor.Research finds can prepare by KOH active oxidation Graphene the absorbent charcoal material (activation Graphene) of high-specific surface area.In the process of KOH activation, due to the corrosive nature of KOH, in graphene oxide, introduce the hole of a large amount of nano-scales, finally form the Graphene tridimensional network of porous.Graphene oxide is after overactivation, and conductivity is improved, and power density is also very high, and in electrolyte solution, cyclical stability is fine, capacitive property excellence.But at present preparation activation Graphene is to be difficult to volume production and expensive graphene oxide is raw material, preparation cost is high, therefore limited to a great extent activation Graphene at new device as the application of lithium-ion secondary cell and ultracapacitor.
Summary of the invention
The object of the present invention is to provide a kind of activation graphene film and preparation method thereof, the activation graphene film good conductivity making, specific surface area is large, and mesopore content is many, and impurity is few; Preparation cost is low, equipment investment is few, simple to operate, easily realizes industrialization; Chemical property is good, and physical and chemical stability is good; The deficiency of having avoided the aspect such as cost costliness, poorly conductive that preparation activation graphene film exists taking graphene oxide as raw material, is with a wide range of applications at exploitation and the novel material of the various devices such as ion secondary battery cathode material lithium and electrode material for super capacitor.
For achieving the above object, the present invention adopts following technical scheme:
Taking graphene film as raw material, by adding sulfuric acid, nitric acid and potassium permanganate, graphene film is carried out to intercalation processing, then adopt KOH activating process to make activation graphene film.
Preparation method's concrete steps are as follows:
(1) intercalation processing of graphene film
The graphene film of raw material: carbon content >99.0%
Intercalator: potassium permanganate (chemical pure), nitric acid (chemical pure) and sulfuric acid (chemical pure)
Potassium permanganate, nitric acid and sulfuric acid are mixed, add graphene film, stirring reaction, adding concentration is 30% hydrogen peroxide, till not producing bubble, product water is washed till after neutrality to vacuum-drying to solution;
Processing parameter is as follows:
The mass ratio of nitric acid, sulfuric acid and potassium permanganate: 1-5:1-10:0.1-1
The mass ratio of graphene film and intercalator: 1:2-1:20
Graphene film thickness: 1-15 nm
Reaction times: 30-120 min
Stirring velocity: 50-500 rpm
Drying temperature: 50-100 DEG C
Vacuum tightness: 1.0 × 10
-1-1.0 × 10
5pa
Time of drying: 2-10 h;
(2) with the mixing of KOH
Step (1) gained graphene film is mixed with KOH, under room temperature, stir, leave standstill 65 DEG C of dry 24h;
Processing parameter is as follows:
The mass ratio of graphene film and KOH: 1:1-1:10
Room temperature: 15-25 DEG C
Churning time: 1-4 h
Stirring velocity: 50-500 rpm
Time of repose: 8-12 h;
(3) activation
Step (2) gained mixture is packed in corundum crucible, be placed in atmosphere furnace, pass into protective atmosphere, be then warming up to activation temperature with certain temperature rise rate, insulation;
Processing parameter is as follows:
Protective atmosphere: N
2or Ar
Gas flow: 50-200 mL/min
Temperature rise rate: 3-10 DEG C/min
Activation temperature: 600-1000 DEG C
Soaking time: 1-6 h;
(4) washing, dry
In step (3) products therefrom, add hydrochloric acid soln, at 25 DEG C, reaction, is then washed till neutrality with deionized water, vacuum-drying;
Processing parameter is as follows:
The concentration of hydrochloric acid soln: 1-6 mol/L
Reaction times: 1-4 h
Drying temperature: 50-100 DEG C
Vacuum tightness: 1.0 × 10
-1-1.0 × 10
5pa
Time of drying: 4-12 h.
The present invention reaches by controlling intercalation and activating process the object of controlling activation Graphene chip architecture and performance.Adopt the obtained activation Graphene of preparation method of the present invention plate electrode material to there is good chemical property, specific surface area 200-2000m
2/ g, mesoporous 30%-60%, specific conductivity 10
3-10
4s/m, it can reach nearly 140F/g than electric capacity in the time that current density is 0.1A/g, and after discharging and recharging for 2000 times, the rate of loss of electric capacity is very little, has good cyclical stability.Compared with prior art, the advantage that the present invention has and effect are: technique is simple, are easy to produce, easy and simple to handle; Preparation cost is low, and the method obtains activation graphene film, even aperture distribution, and specific surface area is large, and the defect of sample is few, and electroconductibility is high, and capacitive property improves obviously, is suitable for suitability for industrialized production.
Embodiment
Be below several specific embodiment of the present invention, further illustrate the present invention, but the present invention be not limited only to this.
embodiment 1
2:4.5:0.3 takes respectively nitric acid, sulfuric acid, potassium permanganate and puts into reactor and mix and make intercalator in mass ratio, then adding thickness is the graphene film (graphene film and intercalator mass ratio are 1:2) of 10-15nm, stirring 30min(rotary speed 50rpm) to drip concentration in backward reactor be 30% hydrogen peroxide, until do not produce bubble in solution.Graphene film after intercalation processing is washed till to neutrality with deionized water, is placed in the dry 10h(vacuum tightness 1.0 × 10 of 50 DEG C of vacuum drying ovens
5pa).By the graphene film after intercalation processing, according to being that 1:2 mixes with KOH mass ratio, under room temperature condition, stir, rotating speed is adjusted to 500rpm and stirs 4h, leaves standstill 8h, is then placed in 65 DEG C of loft drier inner drying 24h and obtains intercalated graphite alkene sheet.Pack intercalated graphite alkene sheet powder into corundum crucible, be then placed in atmosphere furnace, at N
2protection is lower is raised to 600 DEG C by the temperature rise rate of 5 DEG C/min, and insulation 6h, cools to afterwards room temperature with the furnace and take out, and with deionized water repetitive scrubbing sample, until pH is neutral, then after 100 DEG C of dry 12h, is activation graphene film (vacuum tightness 1.0 × 10
5pa).
Prepared activation graphene film has following performance: specific surface area 220m
2/ g, mesoporous 35%, specific conductivity 1377S/m is 47F/g than electric capacity in the time that current density is 0.1A/g, and the rate of loss of electric capacity is 3% after discharging and recharging for 2000 times.
embodiment 2
1:10:0.5 takes respectively nitric acid, sulfuric acid, potassium permanganate and puts into reactor and mix and make intercalator in mass ratio, then adding thickness is the graphene film (graphene film and intercalator mass ratio are 1:5) of 8-10nm, stirring 120min(rotary speed 200rpm) to drip concentration in backward reactor be 30% hydrogen peroxide, until do not produce bubble in solution.Graphene film after intercalation processing is washed till to neutrality with deionized water, is placed in 100 DEG C of dry 2h(vacuum tightness 1.0Pa in vacuum drying oven).By the graphene film after intercalation processing, according to being that 1:3 mixes with KOH mass ratio, under room temperature condition, stir, rotating speed is adjusted to 200rpm and stirs 1h, leaves standstill 12h, is then placed in 65 DEG C of loft drier inner drying 24h and obtains intercalated graphite alkene sheet.Pack intercalated graphite alkene sheet powder into corundum crucible; then be placed in atmosphere furnace; under Ar protection, be raised to 700 DEG C by the temperature rise rate of 10 DEG C/min; insulation 4h; cooling to afterwards room temperature with the furnace takes out; with deionized water repetitive scrubbing sample, until pH is neutral, then after 80 DEG C of dry 12h, be activation graphene film (vacuum tightness 1.0 × 10
2pa).
Prepared activation graphene film has following performance: specific surface area 450m
2/ g, mesoporous 37%, specific conductivity 2136S/m is 83F/g than electric capacity in the time that current density is 0.1A/g, and the rate of loss of electric capacity is 4% after discharging and recharging for 2000 times.
embodiment 3
5:1:1 takes respectively nitric acid, sulfuric acid, potassium permanganate and puts into reactor and mix and make intercalator in mass ratio, then adding thickness is the graphene film (graphene film and intercalator mass ratio are 1:7) of 2-3nm, stirring 60min(rotary speed 100rpm) to drip concentration in backward reactor be 30% hydrogen peroxide, until do not produce bubble in solution.Graphene film after intercalation processing is washed till to neutrality with deionized water, is placed in 80 DEG C of dry 6h(vacuum tightnesss 1.0 × 10 in vacuum drying oven
3pa).By the graphene film after intercalation processing, according to being that 1:5 mixes with KOH mass ratio, under room temperature condition, stir, rotating speed is adjusted to 300rpm and stirs 2h, leaves standstill 10h, is then placed in 65 DEG C of loft drier inner drying 24h and obtains intercalated graphite alkene sheet.Pack intercalated graphite alkene sheet powder into corundum crucible; then be placed in atmosphere furnace; under Ar protection, be raised to 800 DEG C by the temperature rise rate of 8 DEG C/min; insulation 2h; cooling to afterwards room temperature with the furnace takes out; with deionized water repetitive scrubbing sample, until pH is neutral, then after 60 DEG C of dry 12h, be activation graphene film (vacuum tightness 1.0 × 10
-1pa).
Prepared activation graphene film has following performance: specific surface area 1500m
2/ g, mesoporous 50%, specific conductivity 4300S/m is 140F/g than electric capacity in the time that current density is 0.1A/g, and the rate of loss of electric capacity is 5% after discharging and recharging for 2000 times.
embodiment 4
4:9:0.7 takes respectively nitric acid, sulfuric acid, potassium permanganate and puts into reactor and mix and make intercalator in mass ratio, then adding thickness is the graphene film (graphene film and intercalator mass ratio are 1:10) of 6-7nm, stirring 90min(rotary speed 300rpm) to drip concentration in backward reactor be 30% hydrogen peroxide, until do not produce bubble in solution.Graphene film after intercalation processing is washed till to neutrality with deionized water, is placed in 60 DEG C of dry 6h(vacuum tightnesss 1.0 × 10 in vacuum drying oven
2pa).By the graphene film after intercalation processing, according to being that 1:7 mixes with KOH mass ratio, under room temperature condition, stir, rotating speed is adjusted to 500rpm and stirs 2.5h, leaves standstill 9h, is then placed in 65 DEG C of loft drier inner drying 24h and obtains intercalated graphite alkene sheet.Pack intercalated graphite alkene sheet powder into corundum crucible; then be placed in atmosphere furnace; under Ar protection, be raised to 900 DEG C by the temperature rise rate of 3 DEG C/min; insulation 1h; cooling to afterwards room temperature with the furnace takes out; with deionized water repetitive scrubbing sample, until pH is neutral, then after 80 DEG C of dry 10h, be activation graphene film (vacuum tightness 10Pa).
Prepared activation graphene film has following performance: specific surface area 1200m
2/ g, mesoporous 50%, specific conductivity 4300S/m is 132F/g than electric capacity in the time that current density is 0.1A/g, and the rate of loss of electric capacity is 5% after discharging and recharging for 2000 times.
embodiment 5
3:8:0.5 takes respectively nitric acid, sulfuric acid, potassium permanganate and puts into reactor and mix and make intercalator in mass ratio, then adding thickness is the graphene film (graphene film and intercalator mass ratio are 1:20) of 3-4nm, stirring 60min(rotary speed 250rpm) to drip concentration in backward reactor be 30% hydrogen peroxide, until do not produce bubble in solution.Graphene film after intercalation processing is washed till to neutrality with deionized water, is placed in 100 DEG C of dry 2h(vacuum tightnesss 1.0 × 10 in vacuum drying oven
-1pa).By the graphene film after intercalation processing, according to being that 1:9 mixes with KOH mass ratio, under room temperature condition, stir, rotating speed is adjusted to 300rpm and stirs 1h, leaves standstill 10h, is then placed in 65 DEG C of loft drier inner drying 24h and obtains intercalated graphite alkene sheet.Pack intercalated graphite alkene sheet powder into corundum crucible; then be placed in atmosphere furnace; under Ar protection, be raised to 850 DEG C by the temperature rise rate of 5 DEG C/min; insulation 1.5h; cooling to afterwards room temperature with the furnace takes out; with deionized water repetitive scrubbing sample, until pH is neutral, then after 80 DEG C of dry 10h, be activation graphene film (vacuum tightness 1.0Pa).
Prepared activation graphene film has following performance: specific surface area 2000m
2/ g, mesoporous 30%, specific conductivity 2700S/m is 124F/g than electric capacity in the time that current density is 0.1A/g, and the rate of loss of electric capacity is 12% after discharging and recharging for 2000 times.
The foregoing is only preferred embodiment of the present invention, all equalizations of doing according to the present patent application the scope of the claims change and modify, and all should belong to covering scope of the present invention.
Claims (3)
1. an activation graphene film, is characterized in that: taking graphene film as raw material, by adding sulfuric acid, nitric acid and potassium permanganate, graphene film is carried out to intercalation processing, then adopt KOH activating process to make activation graphene film.
2. a method of preparing activation graphene film as claimed in claim 1, is characterized in that: comprise the intercalation processing of graphene film, with the mixing of KOH, activation, washing, dry.
3. method according to claim 2, is characterized in that: concrete steps are as follows:
(1) intercalation processing of graphene film
The graphene film of raw material: carbon content >99.0%
Intercalator: potassium permanganate, nitric acid and sulfuric acid
Potassium permanganate, nitric acid and sulfuric acid are mixed, add graphene film, stirring reaction, adding concentration is 30% hydrogen peroxide, till not producing bubble, product water is washed till after neutrality to vacuum-drying to solution;
Processing parameter is as follows:
The mass ratio of nitric acid, sulfuric acid and potassium permanganate: 1-5:1-10:0.1-1
The mass ratio of graphene film and intercalator: 1:2-1:20
Graphene film thickness: 1-15 nm
Reaction times: 30-120 min
Stirring velocity: 50-500 rpm
Drying temperature: 50-100 DEG C
Vacuum tightness: 1.0 × 10
-1-1.0 × 10
5pa
Time of drying: 2-10 h;
(2) with the mixing of KOH
Step (1) gained graphene film is mixed with KOH, under room temperature, stir, leave standstill 65 DEG C of dry 24h;
Processing parameter is as follows:
The mass ratio of graphene film and KOH: 1:1-1:10
Room temperature: 15-25 DEG C
Churning time: 1-4 h
Stirring velocity: 50-500 rpm
Time of repose: 8-12 h;
(3) activation
Step (2) gained mixture is packed in corundum crucible, be placed in atmosphere furnace, pass into protective atmosphere, be then warming up to activation temperature with certain temperature rise rate, insulation;
Processing parameter is as follows:
Protective atmosphere: N
2or Ar
Gas flow: 50-200 mL/min
Temperature rise rate: 3-10 DEG C/min
Activation temperature: 600-1000 DEG C
Soaking time: 1-6 h;
(4) washing, dry
In step (3) products therefrom, add hydrochloric acid soln, at 25 DEG C, reaction, is then washed till neutrality with deionized water, vacuum-drying;
Processing parameter is as follows:
The concentration of hydrochloric acid soln: 1-6 mol/L
Reaction times: 1-4 h
Drying temperature: 50-100 DEG C
Vacuum tightness: 1.0 × 10
-1-1.0 × 10
5pa
Time of drying: 4-12 h.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104599863A (en) * | 2015-01-15 | 2015-05-06 | 华东理工大学 | Method for preparation of composite material, composite material and application thereof |
| CN104803380A (en) * | 2015-05-12 | 2015-07-29 | 中国科学院上海微***与信息技术研究所 | Preparation method of graphene |
| CN105810456A (en) * | 2016-05-06 | 2016-07-27 | 北京化工大学 | Activated graphene/needle-shaped nickel hydroxide nanocomposite material and preparation method thereof |
| CN107611399A (en) * | 2017-09-11 | 2018-01-19 | 福建师范大学 | The method that high dispersive graphene improves the nickel-cobalt-manganese ternary material property of Doped ions |
| CN107611400A (en) * | 2017-09-11 | 2018-01-19 | 福建师范大学 | The method that high dispersive graphene improves nickel-cobalt-manganese ternary material electrochemical performance |
| CN107634204A (en) * | 2017-09-11 | 2018-01-26 | 福建师范大学 | The method that high dispersive graphene improves rare earth doped nickel-cobalt-manganese ternary material property |
| CN109292766A (en) * | 2018-12-12 | 2019-02-01 | 天津市职业大学 | A kind of clean preparation method of Activated Graphite alkene |
| CN111628172A (en) * | 2020-05-12 | 2020-09-04 | 山东领军科技集团有限公司 | Production process of graphene-based battery conductive agent |
| CN114835115A (en) * | 2022-05-13 | 2022-08-02 | 宝泰隆新材料股份有限公司北京技术研发中心 | Preparation method and application of active mesophase carbon microspheres |
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| CN102153077A (en) * | 2011-05-12 | 2011-08-17 | 北京工业大学 | Method for preparing single-layer graphene with high carbon-oxygen ratio |
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| CN102153077A (en) * | 2011-05-12 | 2011-08-17 | 北京工业大学 | Method for preparing single-layer graphene with high carbon-oxygen ratio |
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104599863A (en) * | 2015-01-15 | 2015-05-06 | 华东理工大学 | Method for preparation of composite material, composite material and application thereof |
| CN104599863B (en) * | 2015-01-15 | 2017-07-18 | 华东理工大学 | A kind of method for preparing composite, composite and its application |
| CN104803380A (en) * | 2015-05-12 | 2015-07-29 | 中国科学院上海微***与信息技术研究所 | Preparation method of graphene |
| CN104803380B (en) * | 2015-05-12 | 2017-02-22 | 中国科学院上海微***与信息技术研究所 | Preparation method of graphene |
| CN105810456A (en) * | 2016-05-06 | 2016-07-27 | 北京化工大学 | Activated graphene/needle-shaped nickel hydroxide nanocomposite material and preparation method thereof |
| CN107611399A (en) * | 2017-09-11 | 2018-01-19 | 福建师范大学 | The method that high dispersive graphene improves the nickel-cobalt-manganese ternary material property of Doped ions |
| CN107611400A (en) * | 2017-09-11 | 2018-01-19 | 福建师范大学 | The method that high dispersive graphene improves nickel-cobalt-manganese ternary material electrochemical performance |
| CN107634204A (en) * | 2017-09-11 | 2018-01-26 | 福建师范大学 | The method that high dispersive graphene improves rare earth doped nickel-cobalt-manganese ternary material property |
| CN109292766A (en) * | 2018-12-12 | 2019-02-01 | 天津市职业大学 | A kind of clean preparation method of Activated Graphite alkene |
| CN109292766B (en) * | 2018-12-12 | 2021-09-28 | 天津市职业大学 | Clean production method of active graphene |
| CN111628172A (en) * | 2020-05-12 | 2020-09-04 | 山东领军科技集团有限公司 | Production process of graphene-based battery conductive agent |
| CN114835115A (en) * | 2022-05-13 | 2022-08-02 | 宝泰隆新材料股份有限公司北京技术研发中心 | Preparation method and application of active mesophase carbon microspheres |
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Application publication date: 20140917 |