CN103515608A - Graphene/sulfur composite material and preparation method thereof, battery positive electrode and preparation method thereof, and battery - Google Patents
Graphene/sulfur composite material and preparation method thereof, battery positive electrode and preparation method thereof, and battery Download PDFInfo
- Publication number
- CN103515608A CN103515608A CN201210215742.7A CN201210215742A CN103515608A CN 103515608 A CN103515608 A CN 103515608A CN 201210215742 A CN201210215742 A CN 201210215742A CN 103515608 A CN103515608 A CN 103515608A
- Authority
- CN
- China
- Prior art keywords
- graphene
- composite material
- preparation
- battery
- sulphur composite
- 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
-
- 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
-
- 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 invention belongs to the field of electrochemistry, and discloses a graphene/sulfur composite material and a preparation method thereof, a battery positive electrode and a preparation method thereof, and a battery. The graphene/sulfur composite material comprises graphene and elemental sulfur at a mass ratio of (1-5):(5-9), moreover, the elemental sulfur is embedded into the microcellular structure of the graphene. According to the graphene/sulfur composite material provided by the invention, the elemental sulfur is embedded into the microcellular structure of the graphene, a graphene/elemental sulfur composite material is prepared, the microcellular structure of the graphene with high specific surface area can prevent loss of a discharging product of sulfur, so that the solubility is reduced; meanwhile, since the graphene has high conductivity and is fully contacted with the elemental sulfur, the conductivity of a sulfur electrode is improved.
Description
Technical field
The present invention relates to electrochemical material, relate in particular to a kind of Graphene/sulphur composite material and preparation method thereof.The invention still further relates to a kind of this Graphene/sulphur composite material that uses as anode of positive electrode active materials and preparation method thereof.The invention still further relates to a kind of battery that uses described anode.
Background technology
Along with the development of various new forms of energy, the miniaturization development of portable electric appts and the widespread demand of electric automobile to large-capacity high-power chemical power source.Current commercial lithium ion battery adopts inorganic positive pole/graphite system mostly, and wherein these positive electrodes are mainly LiFePO4s, LiMn2O4, cobalt acid lithium, the system of lithium nickelate and mixing.Although the chemical property of this class system is excellent, due to itself capacity lower (as the theoretical 170mAh/g of LiFePO4), complicated process of preparation, the shortcoming that high in cost of production is many.So the positive electrode of other kind of development of new has been subject to people's attention widely.
The advantages such as the elemental sulfur of usining has high theoretical specific capacity and specific energy as the lithium-sulfur cell system of positive electrode, cheap, and environmental pollution is little, had been subject to paying close attention to widely in the last few years, were one of positive electrodes the most competitive in lithium battery of future generation.But due to the insulation characterisitic of elemental sulfur, (room-temperature conductivity is 5 * 10
-30s/cm) and the highly dissoluble of its discharging product in organic electrolyte, hindered the commercialization process of lithium-sulfur cell.There are some researches show the performance that can effectively improve sulfur electrode by the compound method of sulphur carbon, this is the conductivity that can suppress the dissolving of discharging product and improve sulfur electrode due to the high-specific surface area of material with carbon element and absorption property, thereby improves the utilance of active material and the cycle performance of battery.
Summary of the invention
Based on the problems referred to above, problem to be solved by this invention is to provide a kind of Graphene/sulphur composite material.
Technical scheme of the present invention is as follows:
/ sulphur composite material, comprise that mass ratio is Graphene and the elemental sulfur of 1 ~ 5:5 ~ 9, and elemental sulfur is embedded in the microcellular structure of Graphene.
The preparation method of above-mentioned Graphene/sulphur composite material, comprises the steps:
S1, Graphene and elemental sulfur (preferably 100 object elemental sulfurs) are ground 2 ~ 5 hours according to the ratio of mass ratio 1 ~ 5:5 ~ 9, obtain mixed powder; Grinding can select agate mortar or ball mill to carry out, preferred spheres grinding machine;
In S2, oxygen-free environment, mixed powder is first placed at 170 ℃ to heat preservation sintering 6 hours, is warming up to subsequently 280 ℃, then heat preservation sintering 3 hours, be finally cooled to room temperature, obtain described Graphene/sulphur composite material; Heat preservation sintering process is to carry out in vacuum tube furnace.
The preparation method of described Graphene/sulphur composite material, in step S1, described Graphene adopts following steps to make:
S11, graphite oxide is placed in to the ultrasonic 1 ~ 5h of water, obtains the suspension that concentration is 0.1 ~ 20g/L;
S12, the KOH solution that is 0.1 ~ 10mol/L by concentration join in above-mentioned suspension, stir, and obtain condensation product; Wherein, the mass ratio of KOH and graphite oxide is 1 ~ 30:1;
S13, filter condensation product, 60 ~ 80 ℃ of dry 24 ~ 48h, obtain pressed powder, then pressed powder are put into Muffle furnace, 800 ~ 1200 ℃ of reaction 1 ~ 5h, cooling after, washing, dryly obtain described Graphene.
The present invention also provides a kind of anode, comprises aluminium foil and is coated in the positive electrode on aluminium foil, and wherein, described positive electrode comprises that mass ratio is above-mentioned Graphene/sulphur composite material, Kynoar binding agent and the acetylene black of 85:5:10.
The preparation method of above-mentioned anode, comprises the steps:
Graphene/sulphur composite material, Kynoar binding agent and acetylene black that A1, mass ratio are 85:5:10 mix, and make slurry;
A2, slurry is coated on aluminium foil, drying, roll film, trimming is processed, and makes anode.
The present invention also provides a kind of battery, the above-mentioned anode of positive pole of this battery; The assembling of this battery is as follows:.
By positive pole, barrier film, negative pole in order stacked group dress up battery core, then use battery housing seal battery core, by the liquid injection port being arranged on battery container, in battery container, inject electrolyte subsequently, sealing liquid injection port, obtains battery; This battery is lithium-sulfur cell.
In above-mentioned lithium-sulfur cell, the solute electrolyte in electrolyte adopts LiPF
6, LiBF
4, LiTFSI (LiN (SO
2cF
3)
2) or LiFSI (LiN (SO
2f)
2) etc.; The concentration of electrolyte is generally 1mol/L; Solvent adopts one or more mixing in dimethyl carbonate, diethyl carbonate, propene carbonate, ethylene carbonate and acetonitrile.
Graphene/sulphur composite material provided by the invention, elemental sulfur is embedded in the microcellular structure of Graphene, has prepared Graphene/elemental sulfur composite material, and the microcellular structure of the Graphene of high-specific surface area can prevent the loss of the discharging product of sulphur, has reduced dissolubility; Simultaneously due to the high conductivity of Graphene and with elemental sulfur fully contact the conductivity that has improved sulfur electrode.
Accompanying drawing explanation
Fig. 1 is the battery structure schematic diagram of embodiment 5.
Embodiment
Below in conjunction with accompanying drawing, preferred embodiment of the present invention is described in further detail.
Embodiment 1 ~ 4th, the preparation method of Graphene/sulphur composite material, and embodiment 5 ~ 8th, and material prepared by the embodiment 1 ~ 4 of usining is as the application of lithium-sulphur cell positive electrode.
Embodiment 1
1, the preparation of Graphene:
(1) graphite oxide is placed in to the ultrasonic 1h of water, obtains the suspension that concentration is 0.1g/L,
(2) the KOH solution that configuration concentration is 0.1mol/L, joins KOH solution in above-mentioned suspension, stirs until there is condensation product, and wherein the quality of KOH and graphite oxide is respectively 10g and 10g;
(3) condensation product obtained above is filtered, 60 ℃ of dry 48h, obtain pressed powder, then pressed powder are put into Muffle furnace, 800 ℃ of reaction 5h, cooling after, washing, the dry Graphene that obtains high-specific surface area.
2, the preparation of Graphene/sulphur composite material:
The 6g Graphene obtaining and 6g elemental sulfur (100 orders are analyzed pure) are fully ground evenly in agate mortar.Then put into ball mill ball milling 2 hours.Mixture after grinding is put into vacuum tube furnace, in lasting nitrogen or argon shield atmosphere, be first warmed up to 170 ℃, be incubated 6 hours.Then temperature is controlled to 280 ℃ of left and right, is incubated 3 hours, can obtain sulfur mass fraction 50% Graphene/sulphur composite material.
Embodiment 2
1, the preparation of Graphene:
(1) graphite oxide is placed in to the ultrasonic 5h of water, obtains the suspension that concentration is 20g/L,
(2) the KOH solution that configuration concentration is 10mol/L, joins KOH solution in above-mentioned suspension, stirs until there is condensation product, and wherein the quality of KOH and graphite oxide is respectively 300g and 10g;
(3) condensation product obtained above is filtered, 80 ℃ of dry 24h, obtain pressed powder, then pressed powder are put into Muffle furnace, 1200 ℃ of reaction 1h, cooling after, washing, the dry Graphene that obtains high-specific surface area.
2, the preparation of Graphene/sulphur composite material:
The 6g Graphene obtaining and 54g elemental sulfur (100 orders are analyzed pure) are fully ground evenly in agate mortar.Then put into ball mill ball milling 5 hours.Mixture after grinding is put into vacuum tube furnace, in lasting nitrogen or argon shield atmosphere, be first warmed up to 170 ℃, be incubated 6 hours.Then temperature is controlled to 280 ℃ of left and right, is incubated 3 hours, can obtain sulfur mass fraction 90% Graphene/sulphur composite material.
Embodiment 3
1, the preparation of Graphene:
(1) graphite oxide is placed in to the ultrasonic 2h of water, obtains the suspension that concentration is 10g/L,
(2) the KOH solution that configuration concentration is 2mol/L, joins KOH solution in above-mentioned suspension, stirs until there is condensation product, and wherein the quality of KOH and graphite oxide is respectively 50g and 10g;
(3) condensation product obtained above is filtered, 70 ℃ of dry 36h, obtain pressed powder, then pressed powder are put into Muffle furnace, 900 ℃ of reaction 4h, cooling after, washing, the dry Graphene that obtains high-specific surface area.
2, the preparation of Graphene/sulphur composite material:
The 6g graphene with high specific surface obtaining and 9g elemental sulfur (100 orders are analyzed pure) are fully ground evenly in agate mortar.Then put into ball mill ball milling 3 hours.Mixture after grinding is put into vacuum tube furnace, in lasting nitrogen or argon shield atmosphere, be first warmed up to 170 ℃, be incubated 6 hours.Then temperature is controlled to 280 ℃ of left and right, is incubated 3 hours, can obtain sulfur mass fraction 60% Graphene/sulphur composite material.
Embodiment 4
1, the preparation of Graphene:
(1) graphite oxide is placed in to the ultrasonic 3h of water, obtains the suspension that concentration is 15g/L,
(2) the KOH solution that configuration concentration is 5mol/L, joins KOH solution in above-mentioned suspension, stirs until there is condensation product, and wherein the quality of KOH and graphite oxide is respectively 150g and 10g;
(3) condensation product obtained above is filtered, 65 ℃ of dry 40h, obtain pressed powder, then pressed powder are put into Muffle furnace, 1000 ℃ of reaction 3h, cooling after, washing, the dry Graphene that obtains high-specific surface area.
2, the preparation of Graphene/sulphur composite material:
The 6g Graphene obtaining and 14g elemental sulfur (100 orders are analyzed pure) are fully ground evenly in agate mortar.Then put into ball mill ball milling 4 hours.Mixture after grinding is put into vacuum tube furnace, in lasting nitrogen or argon shield atmosphere, be first warmed up to 170 ℃, be incubated 6 hours.Then temperature is controlled to 280 ℃ of left and right, is incubated 3 hours, can obtain sulfur mass fraction 70% Graphene/sulphur composite material.
Graphene/sulphur Electrical Conductivity of Composites to embodiment 1 ~ 4 preparation is tested, and test result is as shown in table 1.
Table 1 Graphene/sulphur Electrical Conductivity of Composites
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | |
| Conductivity 10 -5S/cm | 5.2 | 0.6 | 1.1 | 0.9 |
As shown in Table 1, the composite material that Graphene and sulphur are compound, (room-temperature conductivity is 5 * 10 to the relative elemental sulfur of its conductance
-30s/cm) be significantly improved, the material of this high conductivity is conducive to carry out fast charging and discharging.
Embodiment 5
1, prepare anode
This anode comprises Graphene/sulphur composite material of embodiment 1 preparation;
First, the ratio that is 85:5:10 according to mass ratio, 8.5g Graphene/sulphur composite material, 0.5g Kynoar binding agent and 1g conductive agent acetylene black are mixed, obtain slurry;
Subsequently, slurry is coated on aluminium foil, drying, roll film, trimming is processed, and makes anode, that is to say lithium-sulphur cell positive electrode.
2, preparation battery cathode
Selecting is done negative pole by metal lithium sheet.
3, the assembling of battery
By positive pole, barrier film, negative pole in order stacked group dress up battery core, then use battery housing seal battery core, subsequently by being arranged on liquid injection port on battery container toward the LiPF that injects 1mol/L in battery container
6the electrolyte of/dimethyl carbonate, sealing liquid injection port, obtains battery, is also lithium-sulfur cell; Its structure is positive pole 1, barrier film 3, negative pole 2, battery container 5 and electrolyte 4, as shown in Figure 1.
Embodiment 6
1, prepare anode
This anode comprises Graphene/sulphur composite material of embodiment 2 preparations;
First, the ratio that is 85:5:10 according to mass ratio, 10g Graphene/sulphur composite material, 0.59g Kynoar binding agent and 1.18g conductive agent acetylene black are mixed, obtain slurry;
Subsequently, slurry is coated on aluminium foil, drying, roll film, trimming is processed, and makes lithium-sulphur cell positive electrode.
2, preparation battery cathode
Select metal lithium sheet to do negative pole.
3, the assembling of lithium-sulfur cell
By positive pole, barrier film, negative pole in order stacked group dress up battery core, then use battery housing seal battery core, subsequently by being arranged on liquid injection port on battery container toward the LiBF that injects 1mol/L in battery container
4/ diethyl carbonate electrolyte, sealing liquid injection port, obtains battery, is also lithium-sulfur cell.
Embodiment 7
1, prepare anode
This anode comprises Graphene/sulphur composite material of embodiment 3 preparations;
First, the ratio that is 85:5:10 according to mass ratio, 9g graphene composite material, 0.53g Kynoar binding agent and 1.06g conductive agent acetylene black are mixed, obtain slurry;
Subsequently, slurry is coated on aluminium foil, drying, roll film, trimming is processed, and makes lithium-sulphur cell positive electrode.
2, preparation battery cathode
Select metal lithium sheet to do negative pole.
3, the assembling of lithium-sulfur cell
By positive pole, barrier film, negative pole in order stacked group dress up battery core, use again battery housing seal battery core, subsequently by being arranged on liquid injection port on battery container toward the LiTFSI/ propene carbonate electrolyte that injects 1mol/L in battery container, sealing liquid injection port, obtaining battery, is also lithium-sulfur cell.
Embodiment 8
1, prepare anode
This anode comprises Graphene/sulphur composite material of embodiment 4 preparations;
First, the ratio that is 85:5:10 according to mass ratio, stone 8g China ink alkene composite material, 4.71g Kynoar binding agent and 9.41g conductive agent acetylene black are mixed, obtain slurry;
Subsequently, slurry is coated on aluminium foil, drying, roll film, trimming is processed, and makes lithium-sulphur cell positive electrode.
2, preparation battery cathode
Select metal lithium sheet to do negative pole.
3, the assembling of battery
By positive pole, barrier film, negative pole in order stacked group dress up battery core, use again battery housing seal battery core, subsequently by being arranged on liquid injection port on battery container toward the LiFSI/ ethylene carbonate+acetonitrile electrolyte that injects 1mol/L in battery container, sealing liquid injection port, obtaining battery, is also lithium-sulfur cell.
The battery that embodiment 5 ~ 8 is made carries out charge-discharge test, and test result is as shown in table 2.
The charge-discharge test result of table 2 battery
As shown in Table 2, adopt Graphene/sulphur composite material as anode, its 10 charge and discharge cycles capacity are the circulating battery capacity 10% as anode higher than elemental sulfur; Therefore, Graphene/sulphur composite material is as anode, and the cycle life of battery is largely increased.
Should be understood that, the above-mentioned statement for preferred embodiment of the present invention is comparatively detailed, can not therefore think the restriction to scope of patent protection of the present invention, and scope of patent protection of the present invention should be as the criterion with claims.
Claims (6)
1. Graphene/sulphur composite material, is characterized in that, in this composite material, comprise that mass ratio is Graphene and the elemental sulfur of 1 ~ 5:5 ~ 9, and elemental sulfur is embedded in the microcellular structure of Graphene.
2. a preparation method for Graphene/sulphur composite material, is characterized in that, comprises the steps:
S1, Graphene and elemental sulfur are ground 2 ~ 5 hours according to the ratio of mass ratio 1 ~ 5:5 ~ 9, obtain mixed powder;
In S2, oxygen-free environment, mixed powder is first placed at 170 ℃ to heat preservation sintering 6 hours, is warming up to subsequently 280 ℃, then heat preservation sintering 3 hours, be finally cooled to room temperature, obtain described Graphene/sulphur composite material.
3. the preparation method of Graphene/sulphur composite material according to claim 2, is characterized in that, in step S 1, described Graphene adopts following steps to make:
S11, graphite oxide is placed in to the ultrasonic 1 ~ 5h of water, obtains the suspension that concentration is 0.1 ~ 20g/L;
S12, the KOH solution that is 0.1 ~ 10mol/L by concentration join in above-mentioned suspension, stir, and obtain condensation product; Wherein, the mass ratio of KOH and graphite oxide is 1 ~ 30:1;
S13, filter condensation product, 60 ~ 80 ℃ of dry 24 ~ 48h, obtain pressed powder, then pressed powder are put into Muffle furnace, 800 ~ 1200 ℃ of reaction 1 ~ 5h, cooling after, washing, dryly obtain described Graphene.
4. an anode, comprises aluminium foil and is coated in the positive electrode on aluminium foil, it is characterized in that, described positive electrode comprises that mass ratio is Graphene/sulphur composite material claimed in claim 1, Kynoar binding agent and the acetylene black of 85:5:10.
5. a preparation method for anode as claimed in claim 4, is characterized in that, comprises the steps:
Graphene/sulphur composite material, Kynoar binding agent and acetylene black that A1, mass ratio are 85:5:10 mix, and make slurry;
A2, slurry is coated on aluminium foil, drying, roll film, trimming is processed, and makes anode.
6. a battery, is characterized in that, the positive pole of described battery adopts anode claimed in claim 5.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210215742.7A CN103515608A (en) | 2012-06-27 | 2012-06-27 | Graphene/sulfur composite material and preparation method thereof, battery positive electrode and preparation method thereof, and battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210215742.7A CN103515608A (en) | 2012-06-27 | 2012-06-27 | Graphene/sulfur composite material and preparation method thereof, battery positive electrode and preparation method thereof, and battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103515608A true CN103515608A (en) | 2014-01-15 |
Family
ID=49897967
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210215742.7A Pending CN103515608A (en) | 2012-06-27 | 2012-06-27 | Graphene/sulfur composite material and preparation method thereof, battery positive electrode and preparation method thereof, and battery |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103515608A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104752725A (en) * | 2015-03-16 | 2015-07-01 | 山东玉皇新能源科技有限公司 | Cathode material for high-capacity graphene lithium sulphur battery and preparation method of cathode material |
| CN104752682A (en) * | 2015-03-16 | 2015-07-01 | 山东玉皇新能源科技有限公司 | Preparation method of sulphur/carbon composite cathode material for lithium sulphur battery |
| CN104795543A (en) * | 2015-04-10 | 2015-07-22 | 天津工业大学 | Novel attapulgite-based sulfur composite material, as well as preparation method and energy storage application thereof |
| CN105591076A (en) * | 2014-10-22 | 2016-05-18 | 深圳华粤宝电池有限公司 | A preparing method of a graphene sulfo-based composite material |
| CN106129386A (en) * | 2016-09-09 | 2016-11-16 | 广西大学 | A kind of graphene coated micropore Bombyx mori L. sulfur composite positive pole and preparation method |
| CN111900402A (en) * | 2020-07-29 | 2020-11-06 | 肇庆市华师大光电产业研究院 | Universal electrode material for lithium-sulfur battery and preparation method thereof |
| US11437620B2 (en) * | 2014-02-17 | 2022-09-06 | William Marsh Rice University | Laser induced graphene materials and their use in electronic devices |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102070140A (en) * | 2011-02-28 | 2011-05-25 | 无锡第六元素高科技发展有限公司 | Method for preparing high-specific surface area graphene material by utilizing strong base chemical treatment |
| CN102280630A (en) * | 2011-07-04 | 2011-12-14 | 中国科学院过程工程研究所 | Sulphur-graphene composite cathode material and manufacturing method thereof |
| CN102368553A (en) * | 2011-10-13 | 2012-03-07 | 上海交通大学 | Sulfur-base composite material containing graphene and preparation method thereof |
-
2012
- 2012-06-27 CN CN201210215742.7A patent/CN103515608A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102070140A (en) * | 2011-02-28 | 2011-05-25 | 无锡第六元素高科技发展有限公司 | Method for preparing high-specific surface area graphene material by utilizing strong base chemical treatment |
| CN102280630A (en) * | 2011-07-04 | 2011-12-14 | 中国科学院过程工程研究所 | Sulphur-graphene composite cathode material and manufacturing method thereof |
| CN102368553A (en) * | 2011-10-13 | 2012-03-07 | 上海交通大学 | Sulfur-base composite material containing graphene and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| JIA-ZHAO WANG等: "Sulfur-graphene composite for rechargeable lithium batteries", 《JOURNAL OF POWER SOURCES》 * |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11437620B2 (en) * | 2014-02-17 | 2022-09-06 | William Marsh Rice University | Laser induced graphene materials and their use in electronic devices |
| CN105591076A (en) * | 2014-10-22 | 2016-05-18 | 深圳华粤宝电池有限公司 | A preparing method of a graphene sulfo-based composite material |
| CN104752725A (en) * | 2015-03-16 | 2015-07-01 | 山东玉皇新能源科技有限公司 | Cathode material for high-capacity graphene lithium sulphur battery and preparation method of cathode material |
| CN104752682A (en) * | 2015-03-16 | 2015-07-01 | 山东玉皇新能源科技有限公司 | Preparation method of sulphur/carbon composite cathode material for lithium sulphur battery |
| CN104752682B (en) * | 2015-03-16 | 2017-11-14 | 山东玉皇新能源科技有限公司 | A kind of sulphur of lithium-sulfur cell/carbon composite anode material preparation method |
| CN104795543A (en) * | 2015-04-10 | 2015-07-22 | 天津工业大学 | Novel attapulgite-based sulfur composite material, as well as preparation method and energy storage application thereof |
| CN104795543B (en) * | 2015-04-10 | 2017-11-14 | 天津工业大学 | A kind of concave convex rod base sulphur composite and preparation method thereof and stored energy application |
| CN106129386A (en) * | 2016-09-09 | 2016-11-16 | 广西大学 | A kind of graphene coated micropore Bombyx mori L. sulfur composite positive pole and preparation method |
| CN106129386B (en) * | 2016-09-09 | 2018-10-16 | 广西大学 | A kind of graphene coated micropore silkworm excrement sulphur composite positive pole and preparation method |
| CN111900402A (en) * | 2020-07-29 | 2020-11-06 | 肇庆市华师大光电产业研究院 | Universal electrode material for lithium-sulfur battery and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102790217B (en) | Carbon cladded ferriferrous oxide negative electrode material of lithium ion battery and preparation method thereof | |
| CN103337631B (en) | Improve lithium titanate high-rate discharge ability and suppress the carbon nitrogen of aerogenesis to be total to method for coating | |
| CN102088086B (en) | Method for preparing high-voltage lithium ion battery anode | |
| CN103700820B (en) | A kind of lithium ion selenium battery with long service life | |
| CN102867940B (en) | Process for preparing lithium sulfur battery modified anode | |
| CN102074692B (en) | Preparation method for similar graphene doped lithium ion battery positive electrode material | |
| CN103855389A (en) | Ferric (III) fluoride / carbon composite material and its preparation method and application | |
| CN103515608A (en) | Graphene/sulfur composite material and preparation method thereof, battery positive electrode and preparation method thereof, and battery | |
| CN103050295B (en) | A kind of lithium-ion capacitor | |
| CN102916195B (en) | Graphene-coated copper oxide composite cathode material and method for manufacturing same | |
| CN103606642B (en) | A kind of preparation method of conjugation organic frame compound/sulphur composite material and application | |
| CN103050694B (en) | A kind of positive electrode active materials and preparation method thereof, battery | |
| CN102082259A (en) | Lithium secondary battery electrodes and production method thereof | |
| CN109461906B (en) | Preparation method of lithium-sulfur battery positive electrode material | |
| CN103515595A (en) | Sulfur/polypyrrole-graphene composite material, preparation method thereof, battery positive electrode and lithium-sulfur battery | |
| CN104600247A (en) | Sulfur-carbon composite positive electrode material for lithium-sulfur battery and preparation method of sulfur-carbon composite positive electrode material | |
| CN104051695A (en) | Polymer modified diaphragm for lithium sulphur battery, preparation method of polymer modified diaphragm and lithium sulphur battery | |
| CN103515111A (en) | Lithium ion capacitor positive plate and manufacturing method thereof, lithium ion capacitor and manufacturing method thereof | |
| CN103050732B (en) | Lithium titanate-based chemical power supply | |
| CN103427068B (en) | A kind of positive electrode and preparation method thereof for lithium-sulfur cell | |
| CN102623676A (en) | Composite material for positive pole of lithium-sulfur battery, and positive pole and battery both made of same | |
| CN109950487A (en) | A kind of lithium sulfur battery anode material and preparation method thereof | |
| CN106876699A (en) | A kind of combination electrode and its preparation and application | |
| CN103000874A (en) | Preparation method of carbon-coated ternary positive electrode material | |
| CN101262056A (en) | A water solution chargeable lithium ion battery |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20140115 |
|
| WD01 | Invention patent application deemed withdrawn after publication |