CN101373667A - High potential super capacitor electrode material and preparing method thereof - Google Patents
High potential super capacitor electrode material and preparing method thereof Download PDFInfo
- Publication number
- CN101373667A CN101373667A CN 200810046091 CN200810046091A CN101373667A CN 101373667 A CN101373667 A CN 101373667A CN 200810046091 CN200810046091 CN 200810046091 CN 200810046091 A CN200810046091 A CN 200810046091A CN 101373667 A CN101373667 A CN 101373667A
- Authority
- CN
- China
- Prior art keywords
- electrode material
- carbon
- super capacitor
- high potential
- description
- 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.)
- Granted
Links
Images
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Landscapes
- Electric Double-Layer Capacitors Or The Like (AREA)
Abstract
The invention relates to a high potential supercapacitor electrode material and a preparation method thereof, and belongs to the material and energy resource filed. The supercapacitor electrode material contains elements of C, Fe and P, the mass content of C is less than 10 percent, and other elements can be added as required. The working potential relative to Li<plus>Li can reach 4.3V and has good circulation stability. A matter containing C is added to a precursor, and the forming process of the material is utilized to synthesize and prepare the supercapacitor electrode material. The supercapacitor electrode material contains the elements of C, Fe and P, and can improve the compaction density of the C material and the working potential of the supercapacitor, thereby improving the capacity, the energy response and the power characteristics of the supercapacitor. Compared with the prior art, the method is convenient to operate, and the preparation process is simple and practical. The performance of the supercapacitor can be improved through the improvement of the compaction density and the working potential of the electrode material.
Description
Technical field
The present invention relates to a kind of high potential super capacitor electrode material and preparation method thereof, contain the preparation method of the electrode material for super capacitor of C, Fe and P especially simultaneously, belong to material and energy field.
Background technology
Ultracapacitor (Supercapacitors or Super Capacitors or Ultra Capacitors), can be described as capacitor with super capacity or electrochemical capacitor again, commercial name is also referred to as (Huang) gold capacitor device (Gold Capacitors), storage capacitor or farad capacitor, be to occur along with the development of the breakthrough of material science and electronic product in recent years and fast-developing a kind of novel electronic components of high power, mainly comprise double-layer capacitor and faraday's pseudocapacity capacitor, two electrodes do not constitute mixed capacitor simultaneously.In energy diagram, it has filled up the blank between traditional capacitor and the battery, have the big and high advantage of energy content of battery density of traditional capacitor power density concurrently, capacity can be changed to thousands of farads from several farads, the electric current that sparks can reach thousands of amperes, also have principle and simple in structure, abundant raw material, clean and safe, efficiency for charge-discharge height simultaneously, have extended cycle life, safe and reliable, the scope of application is wide etc. advantage, be to improve and solve the applicable breakthrough components and parts of electric energy dynamic property.Ultracapacitor has huge using value and market potential in fields such as automobile (particularly hybrid vehicle, electric automobile, fuel cell car and exceptional load vehicle), automobile subsystem (as ejecting airbag, tightening safety belt etc.), solar energy (as street lamp, Navigation Lamp etc.), electric tool, electric welding machine, wind energy, electric power, communication, consumption electronic products (as uninterrupted power supply, equal power power supply, non-maintaining system power supply, memory stand-by power supply), railway, national defence and military weapons, enjoys countries in the world to pay close attention to.
Ultracapacitor mainly relies on the electric double layer principle of electrostatic interaction and redox faraday's pseudocapacity principle to carry out energy storage, and performance is mainly by decisions such as the forming of the manufacturing technology of electrode, electrolyte, diaphragm quality and packaging technologies.The manufacturing technology of electrode comprises the preparation of electrode material and electrode, is a key technology of ultracapacitor.The capacitance C of capacitor
T(F) by the capacitance decision of electrode material, can be by the capacitance C of positive pole
p(F) and the capacitance C of negative pole
n(F) pass through formula
Calculate.Capacitor is in charge and discharge process, and voltage is linear change in time, therefore, is stored in an energy density E (Wsg in the capacitor
-1) and power density P (Wg
-1) respectively can by
Obtain with P=IU/m.In a word, the capacitance of capacitor and the capacitance of electrode material are in close relations, and operating potential is bigger to energy and power characteristic influence.The operating potential of capacitor is not only relevant with the decomposition voltage of electrolyte, and is also relevant with the operating voltage of material, and expectation at present improves the performance of ultracapacitor by the operating voltage that improves electrode material.
The electrode material of ultracapacitor mainly contains material with carbon element, metal oxide, metal hydroxides, polymer, composite material etc. at present, but the operating potential of the electrode material of report is no more than 3.0V more at present.The electrode material that contains P and Fe element simultaneously, especially Li
xFe
yPO
4Or Fe
zP etc., the excellent properties with a lot of uniquenesses is very promising lithium ion battery electrode material.Although have a lot at present toward LiFePO
4Middle carbon dope improves the research of performance, but is to utilize carbon to improve LiFePO
4Conductivity, the content of carbon is lower, and all is to be used for lithium ion battery electrode material, does not also find with respect to Li
+/ Li has the report of the capacitance characteristic of linear voltage-time.
Up to the present, also do not have to find in presoma, to add report and the patent that the synthetic preparation of carbonaceous material contains the electrode material for super capacitor of C, Fe and P element simultaneously, more do not find the report and the patent of related manufacturing processes.
The present invention adds carbonaceous material and provides C by it for product by effective process and approach in presoma, directly utilize the forming process of material to prepare C/Fe
zP or C/Li
xFe
yPO
4Or C/Fe
zP/Li
xFe
yPO
4Deng the electrode material for super capacitor that contains C, Fe and P element simultaneously, make full use of the energy storage mechanism of electric double layer and faraday's pseudocapacity of ultracapacitor; In addition, the compound that contains Fe and P element has simultaneously improved the tap density and the utilance of material with carbon element, simplify C and contained P simultaneously and the preparation technology of the compound of Fe element, the capacitance and the operating potential of electrode material have been improved, thereby capacity, energy response and power characteristic have been improved by its ultracapacitor of forming, help being used in combination of ultracapacitor and lithium ion battery, quicken the extensive use of ultracapacitor.
Summary of the invention
The objective of the invention is in order to overcome the low and not high shortcoming that causes the ultracapacitor poor performance of operating potential owing to the material with carbon element tap density at present, start with from synthetic route and technology, by tap density that improves material with carbon element and capacitance and the operating potential that operating potential improves ultracapacitor, thereby improve the energy response and the power characteristic of ultracapacitor, promote the extensive use of ultracapacitor.
Principle of the present invention is based on the relation of energy storage mechanism, calculation of capacity formula, energy density and the power density and the operating potential of ultracapacitor, in presoma, add carbonaceous material, the means of utilization machinery, physics or chemistry etc. prepare the electrode material of high-tap density and high workload current potential, by the operating potential and the tap density of electrode material raising ultracapacitor, improve the chemical property of ultracapacitor.
The present invention can realize by following technology path:
1) with LiOHH
2O, LiNO
3, Li
2CO
3, Li
3PO
4, LiH
2PO
4, Li
2HPO
4, lithium acetate or lithium halide etc. be the lithium source, molysite or simple substance are source of iron, P, H
3PO
4, NH
4H
2PO
4, (NH
4)
2HPO
4Deng being the phosphorus source, can be part or all of phosphorus source and source of iron also with ferrophosphorus, in presoma, add carbonaceous material (compound that especially refers to powder carbon, granulated carbon or carbon containing), by mechanical activation, (high energy) ball milling, airflow milling, spray drying, sonicated, acid or means such as alkali treatment, complexing presoma is mixed, adopt methods such as rheology phase method, mechanical activation method, reaction comminuting method, spray drying process, spraying cracking process, solid phase method, microwave method, water/pure thermal synthesis method, sol-gel processing, ion-exchange to prepare C/LiFePO
4, C/Li
3Fe
2(PO
4)
3Deng electrode material.
2) be source of iron with molysite or simple substance, phosphorus simple substance is the phosphorus source, can be part or all of phosphorus source and source of iron also with ferrophosphorus, in presoma, add carbonaceous material, adopt the different C/Fe-P electrode materials of forming of method preparation such as rheology phase method, mechanical activation method, reaction comminuting method, spray drying process, spraying cracking process, solid phase method, microwave method, water/pure thermal synthesis method, sol-gel processing, ion-exchange.
3) by in presoma, adding a certain amount of Co, Ni, Cu, Mn, N, Si, Sn, Li, Cr, Ru, Cd, Al, Ti, V, Zr, Zn, Mg, Ca, Ba, Ga, In, Tl, Pt, Pb, Pd, Au, Ag, Na, As, B, F, I, O, elements such as S and Re can adopt methods such as mechanical activation method, reaction comminuting method, rheology phase method, spray drying process, spraying cracking process, solid phase method, microwave method, water/pure thermal synthesis method, sol-gel processing, ion-exchange to prepare C/Fe-Cu-P, C/Fe-Mn-P, C/Fe-Co-P, C/Fe-Ni-P, C/Fe-Ni-Co-P, C/Li-Fe-Cu-PO
4Deng electrode material.
4) can control pattern (especially referring to sphere or sheet shape granule-morphology, three-dimensional or tunnel microstructure etc.), degree of crystallinity and the particle size and the distribution thereof etc. of product by controlling process conditions, also can carry out processing such as certain ball milling or pulverizing as required to product, or product and ferrophosphorus original position are compounded to form the combination electrode material of electrode material/ferrophosphorus, or be masterplate with the product, original positions such as itself and carbon nano-tube, carbon fiber are compounded to form the combination electrode material of electrode material/carbon, also can carry out different modifications to material as required and handle.
The carbonaceous material that the present invention uses comprises carbon containing inorganic matter and carbonaceous organic material, the carbon containing inorganic matter comprises active carbon, carbon fiber, carbon black, acetylene black, graphite, nanostructure carbon, carbon gel, vitreous carbon, carbon cage etc., and carbonaceous organic material comprises citric acid, sucrose, glucose, phenolic resins, polypropylene, polyacrylamide, polyvinyl alcohol, polyethylene glycol etc.
The carbonaceous material that the present invention uses can provide carbon source as product, also can be directly or indirectly for reaction provide protective atmosphere, and protective atmosphere also can be used N
2, Ar, H
2Deng.
Contain C, Fe and P element simultaneously in the high potential super capacitor electrode material of the present invention's preparation, especially refer to C/Fe-P, C/Fe-Cu-P, C/Fe-Mn-P, C/Fe-Ni-P, C/Fe-Co-P, C/Fe-Ni-Co-P, C/LiFePO
4, C/Li
3Fe
2(PO
4)
3, C/Fe-P/LiFePO
4Deng, carbon source, source of iron and phosphorus source there are not special requirement, the mass content of C is between 10～90%.
Can mix one or more elements of O, N, Si, S, B, F, I, Li, Na, K, Cr, Mn, Ni, Co, Ti, Cu, Al, Sn, Ru, Cd, V, Zr, Zn, Mg, Ca, Ba, Ga, In, Tl, Pt, Pb, Pd, Au, Ag and Re etc. of the high potential super capacitor electrode material of the present invention preparation.
The present invention compared with prior art, this method has the following advantages and the high-lighting effect: add carbonaceous material in the reaction precursor body, the forming process preparation that is beneficial to material contains the high potential super capacitor electrode material of C, Fe and P element simultaneously, avoid material with carbon element and contained the independent preparation of Fe, P element compound simultaneously, simplified preparation technology, improved carbon and contained dispersing uniformity in Fe, the P element compound at the same time; The synthetic preparation of the heat electrode material that can utilize the carbonaceous material reaction in the presoma to generate reduces the energy consumption in the material building-up process; The inertia or the reducibility gas that can utilize the carbonaceous material reaction in the presoma to generate provide protective atmosphere for entire reaction; Reduce the cost of present preparation electrode material from the source, realized the comprehensive utilization of energy-conservation of consumption reduction and resource; Can prepare the low cost of special appearance and certain particle size and distribution, contain the high potential super capacitor electrode material of C, Fe and P element simultaneously by the control process conditions; Preparation method's technology is simple, to equipment require low; Easily realize the doping vario-property of other element, improve the performance of material, have more practicality, be easy to large-scale industrial production.
Description of drawings
Fig. 1 is by the C/LiFePO of the present invention's preparation
4The pattern of electrode material for super capacitor.
Fig. 2 is by the C/LiFePO of the present invention's preparation
4The typical constant current charge-discharge curve of the ultracapacitor of assembling.
Fig. 3 is by the C/LiFePO of the present invention's preparation
4The cycle performance of the ultracapacitor of assembling.
Fig. 4 is by the cycle performance of the ultracapacitor of the C/FeCuP assembling of the present invention's preparation.
Embodiment
The invention will be further described below in conjunction with embodiment and accompanying drawing, but the present invention is not limited to following example, and every technical scheme of being made based on technology basic thought of the present invention that modification, replacement or change realized all belongs to scope of the present invention.
Adopt the rheological phase reaction method, with phosphorous chemical industry accessory substance ferrophosphorus Fe
1.5P is source of iron and part phosphorus source, adds a certain amount of NH
4H
2PO
4Replenish the phosphorus source, with LiOHH
2O and Li
2CO
3Be mixing lithium source, and adding ethanol and a certain amount of active carbon (specific area〉100m
2/ g), presoma is fully ground to form the rheology phase, after the low temperature preliminary treatment, put into Muffle furnace roasting 5～40h of 400～900 ℃, utilize airborne oxygen as oxygen source, the oxycarbide that burns with C is an inert protective gas, obtains the C/LiFePO of black
4Electrode material, more fluffy, the spherical LiFePO of preparation
4Be distributed in the tiny carbon granule, its pattern as shown in Figure 1.
Above-mentioned C/LiFePO with preparation
4Electrode material is deceived with conductive acetylene and adhesive is that fully mix 75～85:20～5:5～10 by mass ratio, being coated on after evenly sizing mixing on the treated aluminium foil, as work electrode, is to electrode and reference electrode with lithium metal after the economy-combat sheet drying, Celgard2400 is a barrier film, LiPF
6/ EC+DMC is an electrolyte, is assembled into the simulation test device of electrode/barrier film/electrode in the argon gas glove box.Through constant current charge-discharge test, its typical charging and discharging curve as shown in Figure 2, charging/discharging voltage can reach 4.3V, and the capacitance characteristic of good linear voltage-time is arranged, the stable discharging specific capacitance reaches 50F/g under 130C.
Embodiment 2
Adopt sol-gel processing, with Fe (NO
3)
39H
2O is a source of iron, LiH
2PO
4For lithium source and phosphorus source, add a certain amount of polyvinyl alcohol and ethanol and water, under 20～90 ℃, be stirred well to and form the thickness colloid, after further low temperature preliminary treatment, put into controlled atmosphere tubular type kiln roasting 5～40h of 400～900 ℃, utilize H
2Be protective gas, finally obtain the C/LiFePO of black
4Electrode material.
Utilize the material of preparation to be work electrode, electrochemical property test is with embodiment 1, and operating potential can reach 4.6V, prepared C/LiFePO
4Electrode material has good cycle performance, and the cycle performance under 2C is not decayed through 500 circulation back capacity as shown in Figure 3.
Embodiment 3
Adopting the reaction comminuting method, is source of iron and phosphorus source with ferrophosphorus FeP, with Li
3PO
4Be the lithium source, the ratio of the amount of substance of the two is 2:1, adds a certain amount of sucrose, after high-energy ball milling is handled 15h, puts into controlled atmosphere tubular type kiln roasting 0.5～10h of 200～800 ℃, with N
2Be inert protective gas, utilize oxygen in the sucrose, utilize the forming process of material to make the sucrose carbonization, obtain the controlled black C/Li of carbon content as oxygen source
3Fe
2(PO
4)
3Electrode material.
Utilize the material of preparation to be work electrode, electrochemical property test is with embodiment 1, and operating potential can reach 4.0V, and the stabilization ratio capacitance under 50C can reach 90F/g, and capability retention is 96% after 500 circulations.
Embodiment 4
Adopt spray drying process, with the accessory substance Fe of calcium magnesium phosphate factory
1.7P is source of iron and phosphorus source, at first with Fe
1.7P is crushed to certain particle size with airflow milling, adds a certain amount of Cu powder and carbon black, after the spray-dried processing of presoma, puts into 200～900 ℃ Muffle furnace, and the oxycarbide that burns with C is an inert protective gas, obtains the C/Fe-Cu-P electrode material of black.
Utilize the material of preparation to be work electrode, except that collector with the Copper Foil, other electrochemical property test is with embodiment 1, operating potential can reach 3.6V, the cycle performance under 5C is not decayed through 500 circulation back capacity as shown in Figure 4.
Embodiment 5
Adopting microwave method, is source of iron and phosphorus source with ferrophosphorus FeP, adds a certain amount of MnO
2And polyethylene glycol, after fully mixing, put into microwave oven and heat 30～500min, with H
2Be reduction protection gas, obtain the C/FeMnP electrode material of black.
Utilize the material of preparation to be work electrode, electrochemical property test is with embodiment 4, and operating potential can reach 3.5V, and the stabilization ratio capacitance under 100C can reach 60F/g, and capability retention is 95.6% after 500 circulations.
In sum, the present invention proposes a kind of high potential super capacitor electrode material and preparation method thereof, utilize the forming process preparation of material to contain the electrode material for super capacitor of C, Fe and P simultaneously, good chemical property is arranged, have certain application value by the ultracapacitor of its assembling.
Claims (10)
1. high potential super capacitor electrode material, it is characterized in that: contain C, Fe and P element in the described high potential super capacitor electrode material simultaneously, wherein the mass content of C is not less than 10%.
2. according to the description of claim 1, contain C, Fe and P element in the high potential super capacitor electrode material simultaneously, especially refer to C/Fe-P, C/LiFePO
4, C/Li
3Fe
2(PO
4)
3, C/Fe-P/LiFePO
4, C/Fe-Cu-P, C/Fe-Mn-P, C/Fe-Ni-P, C/Fe-Co-P, C/Fe-Ni-Co-P etc.
3. according to claim 1,2 description, remove C, Fe and P element, can add elements such as O, N, Si, S, B, F, I, Li, Na, K, Cr, Mn, Ni, Co, Ti, Cu, Al, Sn, Ru, Cd, V, Zr, Zn, Mg, Ca, Ba, Ga, In, Tl, Pt, Pb, Pd, Au, Ag and Re in the high workload ultracapacitor potential electrode material.
4. according to the description of claim 1, the mass content of C is between 10～90% in the high potential super capacitor electrode material.
5. the preparation method of high potential super capacitor electrode material according to claim 1, it is characterized in that: in presoma, add carbonaceous material, utilize the forming process of material, synthetic preparation contains the high potential super capacitor electrode material of C, Fe and P element simultaneously.
6. according to the description of claim 5, the carbonaceous material that adds in the presoma comprises carbon containing inorganic matter and carbonaceous organic material.
7. according to the description of claim 5, the forming process of material refers to comprise courses of reaction such as solid phase, liquid phase, gas phase by the preparation process of presoma to product.
8. according to the description of claim 6, the carbon containing inorganic matter comprises active carbon, carbon fiber, carbon black, acetylene black, graphite, nanostructure carbon, carbon gel, vitreous carbon, carbon cage etc., and carbonaceous organic material comprises citric acid, sucrose, glucose, phenolic resins, polypropylene, polyacrylamide, polyvinyl alcohol, polyethylene glycol etc.
9. according to claim 5,6 description, the carbonaceous material that adds in the presoma can provide carbon source for product, also can be directly or indirectly for reaction provide protective atmosphere, and protective atmosphere also can be used N
2, Ar, H
2Deng.
10. according to claim 1,2,3,4,5,6,7,8,9 description, synthesis preparation method can adopt methods such as rheology phase method, sol-gel processing, reaction comminuting method, spray drying process, spraying cracking process, mechanical activation method, solid phase method, microwave method, water/pure thermal synthesis method, ion-exchange, firing method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200810046091 CN101373667B (en) | 2008-09-17 | 2008-09-17 | Preparing method of high potential super capacitor electrode material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200810046091 CN101373667B (en) | 2008-09-17 | 2008-09-17 | Preparing method of high potential super capacitor electrode material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101373667A true CN101373667A (en) | 2009-02-25 |
| CN101373667B CN101373667B (en) | 2010-12-29 |
Family
ID=40447767
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200810046091 Expired - Fee Related CN101373667B (en) | 2008-09-17 | 2008-09-17 | Preparing method of high potential super capacitor electrode material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101373667B (en) |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101748303B (en) * | 2009-12-18 | 2011-11-09 | 四川大学 | Process of preparing FexPyMzM'z' through ferrophosphorus |
| CN101740777B (en) * | 2009-12-18 | 2011-11-09 | 四川大学 | ZnO modified phosphide cathode material and preparation method thereof |
| CN102683694A (en) * | 2011-12-30 | 2012-09-19 | 南昌大学 | Method for preparing LiFePO4/C composite cathode material by using water dissolving-drying method |
| CN103187567A (en) * | 2011-12-31 | 2013-07-03 | 北京有色金属研究总院 | Preparation method of anode material lithium iron (II) phosphate for lithium ion cell |
| CN104701497A (en) * | 2013-12-07 | 2015-06-10 | 天津赫维科技有限公司 | Preparation method of ferrous phosphate Li/C composite material with high specific surface area |
| CN104851599A (en) * | 2015-04-02 | 2015-08-19 | 安徽江威精密制造有限公司 | Composite electrode material with high cycle performance stability and preparation method thereof |
| CN104867689A (en) * | 2015-04-02 | 2015-08-26 | 安徽江威精密制造有限公司 | Waste PVC based electrode material with high energy storage capacity and preparation method thereof |
| CN105321725A (en) * | 2015-10-29 | 2016-02-10 | 南京工程学院 | Micro-nano structure electrode material for super capacitor and preparation method of electrode plate |
| CN105329932A (en) * | 2015-11-24 | 2016-02-17 | 河南师范大学 | Method for large-scale preparation of carbon-doped mixed transition metal oxide porous microspheres |
| CN105914057A (en) * | 2016-05-12 | 2016-08-31 | 广东风华高新科技股份有限公司 | Preparation method of electrode plate |
| CN110648856A (en) * | 2019-09-29 | 2020-01-03 | 广东电网有限责任公司 | Graphene material, preparation method thereof and supercapacitor |
| CN115498142A (en) * | 2022-10-20 | 2022-12-20 | 天津大学 | Self-supporting electrode and preparation method and application thereof |
-
2008
- 2008-09-17 CN CN 200810046091 patent/CN101373667B/en not_active Expired - Fee Related
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101748303B (en) * | 2009-12-18 | 2011-11-09 | 四川大学 | Process of preparing FexPyMzM'z' through ferrophosphorus |
| CN101740777B (en) * | 2009-12-18 | 2011-11-09 | 四川大学 | ZnO modified phosphide cathode material and preparation method thereof |
| CN102683694A (en) * | 2011-12-30 | 2012-09-19 | 南昌大学 | Method for preparing LiFePO4/C composite cathode material by using water dissolving-drying method |
| CN103187567A (en) * | 2011-12-31 | 2013-07-03 | 北京有色金属研究总院 | Preparation method of anode material lithium iron (II) phosphate for lithium ion cell |
| CN103187567B (en) * | 2011-12-31 | 2015-07-22 | 北京有色金属研究总院 | Preparation method of anode material lithium iron (II) phosphate for lithium ion cell |
| CN104701497A (en) * | 2013-12-07 | 2015-06-10 | 天津赫维科技有限公司 | Preparation method of ferrous phosphate Li/C composite material with high specific surface area |
| CN104851599A (en) * | 2015-04-02 | 2015-08-19 | 安徽江威精密制造有限公司 | Composite electrode material with high cycle performance stability and preparation method thereof |
| CN104867689A (en) * | 2015-04-02 | 2015-08-26 | 安徽江威精密制造有限公司 | Waste PVC based electrode material with high energy storage capacity and preparation method thereof |
| CN105321725A (en) * | 2015-10-29 | 2016-02-10 | 南京工程学院 | Micro-nano structure electrode material for super capacitor and preparation method of electrode plate |
| CN105321725B (en) * | 2015-10-29 | 2018-01-05 | 南京工程学院 | A kind of ultracapacitor micro-nano structure electrode material and electrode piece preparation method |
| CN105329932A (en) * | 2015-11-24 | 2016-02-17 | 河南师范大学 | Method for large-scale preparation of carbon-doped mixed transition metal oxide porous microspheres |
| CN105914057A (en) * | 2016-05-12 | 2016-08-31 | 广东风华高新科技股份有限公司 | Preparation method of electrode plate |
| CN110648856A (en) * | 2019-09-29 | 2020-01-03 | 广东电网有限责任公司 | Graphene material, preparation method thereof and supercapacitor |
| CN115498142A (en) * | 2022-10-20 | 2022-12-20 | 天津大学 | Self-supporting electrode and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101373667B (en) | 2010-12-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101373667B (en) | Preparing method of high potential super capacitor electrode material | |
| Liu et al. | High energy and power lithium-ion capacitors based on Mn3O4/3D-graphene as anode and activated polyaniline-derived carbon nanorods as cathode | |
| Gou et al. | Yolk-shell structured V2O3 microspheres wrapped in N, S co-doped carbon as pea-pod nanofibers for high-capacity lithium ion batteries | |
| CN102088074B (en) | Preparation method of anode material of composite silicate | |
| CN101320809B (en) | Lithium ion battery anode material manganese lithium phosphate and preparation method thereof | |
| CN102201576B (en) | Porous carbon in situ composite lithium iron phosphate cathode material and preparation method thereof | |
| CN101789504B (en) | Preparation method of nano LiFel-xMxPO4/C lithium phosphate composite positive pole material | |
| CN109148838B (en) | Anode material of lithium-ion battery and its preparation method and application | |
| US20140106223A1 (en) | METHODS FOR SURFACE COATING OF CATHODE MATERIAL LiNi0.5-XMn1.5MXO4 FOR LITHIUM-ION BATTERIES | |
| CN109103433B (en) | Nitrogen-doped carbon-coated lithium iron phosphate composite material and preparation method thereof | |
| CN103441241A (en) | Preparation method and application of prussian blue complex/carbon composite material | |
| CN103400962A (en) | Spherical LiFePO4/(C+La2/3-xLi3xTiO3) composite anode material and preparation method thereof | |
| CN102496714A (en) | Anode active substance, production method thereof, and lithium ion battery employing anode active substance | |
| CN105140489A (en) | Titanium-doped carbon-coated sodium ferric phosphate material and preparation method thereof | |
| CN109037659A (en) | A kind of preparation method of bilayer carbon-coated LiFePO 4 for lithium ion batteries material | |
| CN103346304A (en) | Tin-carbon composite material for lithium secondary battery negative electrode and preparation method thereof | |
| CN110931781A (en) | Preparation method and application of biomass carbon/sodium iron fluorophosphate composite material | |
| CN102427134A (en) | Mixed conductor composite material LiFePO4-MXy and preparation method thereof | |
| CN102024947A (en) | LiFePO4/Li-Al-O composite positive electrode material and preparation method thereof | |
| CN108281627B (en) | Germanium-carbon composite negative electrode material for lithium ion battery and preparation method thereof | |
| CN102760880A (en) | High power iron phosphate ion battery material and preparation method thereof | |
| CN103515657A (en) | Battery | |
| Huang et al. | Al3+-doped FeNb11O29 anode materials with enhanced lithium-storage performance | |
| CN103199247A (en) | Preparation method of composite positive material with multi-level conductive network of lithium ion battery | |
| CN112768652B (en) | Sodium-manganese-phosphor-ore/carbon composite positive electrode material NaMnPO4Preparation method of/C |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20101229 Termination date: 20120917 |