CN103259012A - Three-dimensional conductive ferroelectric battery K2FeO4Preparation method of/C composite positive electrode material - Google Patents
Three-dimensional conductive ferroelectric battery K2FeO4Preparation method of/C composite positive electrode material Download PDFInfo
- Publication number
- CN103259012A CN103259012A CN2013101788332A CN201310178833A CN103259012A CN 103259012 A CN103259012 A CN 103259012A CN 2013101788332 A CN2013101788332 A CN 2013101788332A CN 201310178833 A CN201310178833 A CN 201310178833A CN 103259012 A CN103259012 A CN 103259012A
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- China
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- feo
- preparation
- positive pole
- composite positive
- potassium ferrate
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- 239000002131 composite material Substances 0.000 title claims abstract description 27
- 238000000034 method Methods 0.000 title claims abstract description 16
- 239000007774 positive electrode material Substances 0.000 title abstract 2
- UMPKMCDVBZFQOK-UHFFFAOYSA-N potassium;iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[K+].[Fe+3] UMPKMCDVBZFQOK-UHFFFAOYSA-N 0.000 claims abstract description 44
- 238000002360 preparation method Methods 0.000 claims abstract description 15
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 9
- 238000002425 crystallisation Methods 0.000 claims abstract description 9
- 230000008025 crystallization Effects 0.000 claims abstract description 9
- 229910021392 nanocarbon Inorganic materials 0.000 claims abstract description 9
- 239000004094 surface-active agent Substances 0.000 claims abstract description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 16
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 230000001590 oxidative effect Effects 0.000 claims description 8
- 238000001953 recrystallisation Methods 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 7
- 239000006230 acetylene black Substances 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 239000002086 nanomaterial Substances 0.000 claims description 5
- 239000002134 carbon nanofiber Substances 0.000 claims description 3
- 238000001523 electrospinning Methods 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 2
- 229920002401 polyacrylamide Polymers 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 3
- 239000013078 crystal Substances 0.000 abstract description 2
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- 238000000975 co-precipitation Methods 0.000 abstract 1
- 238000011065 in-situ storage Methods 0.000 abstract 1
- 230000006837 decompression Effects 0.000 description 6
- 238000007599 discharging Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000010865 sewage Substances 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 235000009814 Luffa aegyptiaca Nutrition 0.000 description 1
- 244000302544 Luffa aegyptiaca Species 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 150000004032 porphyrins Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- PNYYBUOBTVHFDN-UHFFFAOYSA-N sodium bismuthate Chemical compound [Na+].[O-][Bi](=O)=O PNYYBUOBTVHFDN-UHFFFAOYSA-N 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
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- 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
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- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention relates to a three-dimensional conductive ferroelectric cell K2FeO4A preparation method of a/C composite positive electrode material. According to the invention, through an in-situ coprecipitation method, a surfactant and a nano carbon material are added in the crystallization process of potassium ferrate, so that the nano carbon material is embedded into a potassium ferrate crystal to form a three-dimensional conductive composite material. The invention has the advantages of simple process, low material cost and processing cost, simple preparation process, short period, low energy consumption and large-scale production.
Description
Technical field
The present invention relates to a kind of manufacture method of high ferro cell positive pole, especially relate to a kind of three-dimensional conduction high ferro cell K
2FeO
4The preparation method of/C composite positive pole.
Background technology
Be that the battery of positive electrode is called high ferro cell with the compound of sexavalence iron.Potassium ferrate battery has very high theoretical specific capacitance (406 mAh/g), and it has very strong oxidizability, can be used for sewage disposal usually.The discharging product of potassium ferrate is Fe
2O
3NH
2O has flocculation, also can be used for sewage disposal.So potassium ferrate battery is environmentally friendly, it is a kind of green battery.This material can also can be used as the positive electrode of lithium ion battery as the positive pole of alkaline potassium ferrate battery.
Ferrate is as the positive electrode of battery, and in alkaline electrolyte, because the part of potassium ferrate is decomposed, the poorly conductive of its catabolite reduces the utilance of potassium ferrate and discharging efficiency; And because the discharging product poorly conductive of potassium ferrate has hindered ferrate and has been used for secondary cell.
In present disclosed patent and bibliographical information, mainly be the problem of potassium ferrate battery improved stability: by inorganic compound SiO2, ZrO2 or Y
2O
3The ZrO that mixes
2Stability Deng the surface modification potassium ferrate that is coated on potassium ferrate; Also can pass through organic compound 2,3-naphthalene phthalocyanine or porphyrin are coated on the stability of the surface modification potassium ferrate of potassium ferrate.The relevant report of improving potassium ferrate conductivity by the method for mixing or coat is also arranged: by adding a small amount of sodium bismuthate, 2,3-naphthalene phthalocyanine, Y
2O
3The ZrO that mixes
2Improve potassium ferrate conductivity when improving potassium ferrate stability.
Summary of the invention
The purpose of this invention is to provide a kind of three-dimensional conduction high ferro cell K
2FeO
4The preparation method of/C composite positive pole, the K of this method preparation
2FeO
4/ C composite material can improve conductivity and the utilance of potassium ferrate, can enough carry out big multiplying power discharging simultaneously, also can be as the positive pole of secondary cell.Technology of the present invention is simple, material cost and processing cost are low, and preparation technology is simple, the cycle is short, energy consumption is low, can large-scale production.
The present invention is achieved in that a kind of three-dimensional conduction high ferro cell K
2FeO
4/ C composite positive pole preparation method, step is: after preparing the thick product of potassium ferrate by the wet-chemical oxidizing process, before the potassium ferrate recrystallization, in potassium ferrate solution, add certain amount of surfactant and certain amount of nano material with carbon element, add the KOH solution of high concentration again in this solution, make K
2FeO
4The crystallization of/C composite material is separated out.After n-hexane, absolute ethyl alcohol and absolute ether washing, dry through low-temperature reduced-pressure again.
Described nano-carbon material is the mixture of a kind of of acetylene black, conductive black, electrospinning carbon nano-fiber, natural nano material with carbon element etc. or some kinds.
This nano-carbon material shared mass ratio in composite material is between the 0-20%.
Described surfactant can be one or more in softex kw and the polyacrylamide.
The amount of this surfactant can make nano-carbon material be suspended in the solution just.
The concentration of the KOH solution of high concentration is between the 10-16mol/L.
Anode is the battery that contains sexavalence iron oxysalt.
Technique effect of the present invention is: nano-carbon material is dispersed in the potassium ferrate crystal, because hydrophobic effect and the conductive agent of conductive agent contact with ferrate closely, stability and the conductivity of ferrate have been improved, thereby improved the utilance of ferrate positive electrode, also can be used as the positive electrode of secondary cell, potassium ferrate battery is used and development prospect light, had a bright future.
Description of drawings
Fig. 1 is the resulting K of embodiment
2FeO
4The XRD of/C composite powder.
Fig. 2 is the resulting K of embodiment
2FeO
4The SEM of/C composite powder.
Embodiment
Embodiment 1
After preparing the thick product of potassium ferrate by the wet-chemical oxidizing process, before the potassium ferrate recrystallization, in potassium ferrate solution, the acetylene black that adds softex kw and 0.5 gram of 0.01 gram, after treating the softex kw dissolving, add the KOH solution of 12 mol/L again in this solution, make K
2FeO
4The crystallization of/C composite material is separated out.After n-hexane, absolute ethyl alcohol and absolute ether washing, again through room temperature decompression oven dry.
After preparing the thick product of potassium ferrate by the wet-chemical oxidizing process, before the potassium ferrate recrystallization, in potassium ferrate solution, the acetylene black that adds softex kw and 0.5 gram of 0.01 gram, after treating the softex kw dissolving, add the KOH solution of 12 mol/L again in this solution, make K
2FeO
4The crystallization of/C composite material is separated out.After n-hexane, absolute ethyl alcohol and absolute ether washing, again through 50 ℃ of decompression oven dry.
Embodiment 3
After preparing the thick product of potassium ferrate by the wet-chemical oxidizing process, before the potassium ferrate recrystallization, in potassium ferrate solution, add the softex kw of 0.01 gram and the conductive black of 0.5 gram, after treating the softex kw dissolving, add the KOH solution of 12 mol/L again in this solution, make K
2FeO
4The crystallization of/C composite material is separated out.After n-hexane, absolute ethyl alcohol and absolute ether washing, again through 50 ℃ of decompression oven dry.
Embodiment 4
After preparing the thick product of potassium ferrate by the wet-chemical oxidizing process, before the potassium ferrate recrystallization, in potassium ferrate solution, add the softex kw of 0.01 gram and the electrospinning carbon nano-fiber of 0.5 gram, after treating the softex kw dissolving, add the KOH solution of 12 mol/L again in this solution, make K
2FeO
4The crystallization of/C composite material is separated out.After n-hexane, absolute ethyl alcohol and absolute ether washing, again through 50 ℃ of decompression oven dry.
Embodiment 5
After preparing the thick product of potassium ferrate by the wet-chemical oxidizing process, before the potassium ferrate recrystallization, in potassium ferrate solution, add the softex kw of 0.01 gram and the sponge gourd behind high temperature cabonization of 0.5 gram, after treating the softex kw dissolving, add the KOH solution of 12 mol/L again in this solution, make K
2FeO
4The crystallization of/C composite material is separated out.After n-hexane, absolute ethyl alcohol and absolute ether washing, again through 50 ℃ of decompression oven dry.
Embodiment 6
After preparing the thick product of potassium ferrate by the wet-chemical oxidizing process, before the potassium ferrate recrystallization, in potassium ferrate solution, the acetylene black that adds softex kw and 0.5 gram of 0.02 gram, after treating the softex kw dissolving, add the KOH solution of 12 mol/L again in this solution, make K
2FeO
4The crystallization of/C composite material is separated out.After n-hexane, absolute ethyl alcohol and absolute ether washing, again through 50 ℃ of decompression oven dry.
Claims (7)
1. three-dimensional conduction high ferro cell K
2FeO
4The preparation method of/C composite positive pole, after it is characterized in that preparing the thick product of potassium ferrate by the wet-chemical oxidizing process, before the potassium ferrate recrystallization, in potassium ferrate solution, add certain amount of surfactant and certain amount of nano material with carbon element, add the KOH solution of high concentration again in this solution, make K
2FeO
4The crystallization of/C composite material is separated out, and after n-hexane, absolute ethyl alcohol and absolute ether washing, dries through low-temperature reduced-pressure again.
2. three-dimensional conduction high ferro cell K according to claim 1
2FeO
4The preparation method of/C composite positive pole is characterized in that described nano-carbon material is the mixture of a kind of of acetylene black, conductive black, electrospinning carbon nano-fiber, natural nano material with carbon element or some kinds.
3. according to the described three-dimensional conduction high ferro cell K of claim 1
2FeO
4The preparation method of/C composite positive pole is characterized in that the certain amount of nano material with carbon element, and this nano-carbon material shared mass ratio in composite material is between the 0-20%.
4. according to the described three-dimensional conduction high ferro cell K of claim 1
2FeO
4The preparation method of/C composite positive pole is characterized in that described surfactant is one or more in softex kw and the polyacrylamide.
5. three-dimensional conduction high ferro cell K according to claim 1
2FeO
4The preparation method of/C composite positive pole is characterized in that the amount of this surfactant can make nano-carbon material be suspended in the solution just.
6. three-dimensional conduction high ferro cell K according to claim 1
2FeO
4The preparation method of/C composite positive pole is characterized in that the KOH solution of high concentration, and the concentration of this solution is between the 10-16mol/L.
7. three-dimensional conduction high ferro cell K according to claim 1
2FeO
4The preparation method of/C composite positive pole is characterized in that described anode is the battery that contains sexavalence iron oxysalt.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310178833.2A CN103259012B (en) | 2013-05-15 | 2013-05-15 | Three-dimensional conductive ferroelectric battery K2FeO4Preparation method of/C composite positive electrode material |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310178833.2A CN103259012B (en) | 2013-05-15 | 2013-05-15 | Three-dimensional conductive ferroelectric battery K2FeO4Preparation method of/C composite positive electrode material |
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| Publication Number | Publication Date |
|---|---|
| CN103259012A true CN103259012A (en) | 2013-08-21 |
| CN103259012B CN103259012B (en) | 2015-07-22 |
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|---|---|---|---|
| CN201310178833.2A Expired - Fee Related CN103259012B (en) | 2013-05-15 | 2013-05-15 | Three-dimensional conductive ferroelectric battery K2FeO4Preparation method of/C composite positive electrode material |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105047876A (en) * | 2015-07-06 | 2015-11-11 | 江西师范大学 | Preparation method of composite cathode material of ferroelectric battery |
| CN108172792A (en) * | 2017-12-26 | 2018-06-15 | 刘春丽 | A kind of composite cathode material for lithium ion cell and preparation method thereof |
| CN113401948A (en) * | 2021-06-17 | 2021-09-17 | 江西师范大学 | Negative electrode Fe of lithium ion battery7S8/Fe2O3Composite material, preparation method and application |
| CN115382551A (en) * | 2022-07-26 | 2022-11-25 | 湖南大学 | Three-dimensional carbon functional cathode material based on potassium ferrate modification and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101369655A (en) * | 2008-10-07 | 2009-02-18 | 南开大学 | Load type ferrate electrode active material and method of manufacturing the same |
| RU2371392C1 (en) * | 2008-02-12 | 2009-10-27 | Открытое акционерное общество "Корпорация "Росхимзащита" (ОАО "Корпорация "Росхимзащита") | Method of producing potassium ferrate (vi) |
-
2013
- 2013-05-15 CN CN201310178833.2A patent/CN103259012B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2371392C1 (en) * | 2008-02-12 | 2009-10-27 | Открытое акционерное общество "Корпорация "Росхимзащита" (ОАО "Корпорация "Росхимзащита") | Method of producing potassium ferrate (vi) |
| CN101369655A (en) * | 2008-10-07 | 2009-02-18 | 南开大学 | Load type ferrate electrode active material and method of manufacturing the same |
Non-Patent Citations (1)
| Title |
|---|
| 王志涛: "超铁电池：K2FeO4基阴极材料的调制和电池性能", 《中国优秀博硕士学位论文全文数据库（硕士）工程科技Ⅱ辑》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105047876A (en) * | 2015-07-06 | 2015-11-11 | 江西师范大学 | Preparation method of composite cathode material of ferroelectric battery |
| CN108172792A (en) * | 2017-12-26 | 2018-06-15 | 刘春丽 | A kind of composite cathode material for lithium ion cell and preparation method thereof |
| CN113401948A (en) * | 2021-06-17 | 2021-09-17 | 江西师范大学 | Negative electrode Fe of lithium ion battery7S8/Fe2O3Composite material, preparation method and application |
| CN113401948B (en) * | 2021-06-17 | 2022-11-11 | 江西师范大学 | Negative electrode Fe of lithium ion battery 7 S 8 /Fe 2 O 3 Composite material, preparation method and application |
| CN115382551A (en) * | 2022-07-26 | 2022-11-25 | 湖南大学 | Three-dimensional carbon functional cathode material based on potassium ferrate modification and preparation method and application thereof |
| CN115382551B (en) * | 2022-07-26 | 2023-10-13 | 湖南大学 | Three-dimensional carbonaceous functional cathode material based on potassium ferrate modification, and preparation method and application thereof |
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