CN103700858B - Sodium-perfluorocarbon one-shot battery - Google Patents
Sodium-perfluorocarbon one-shot battery Download PDFInfo
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- CN103700858B CN103700858B CN201410006534.5A CN201410006534A CN103700858B CN 103700858 B CN103700858 B CN 103700858B CN 201410006534 A CN201410006534 A CN 201410006534A CN 103700858 B CN103700858 B CN 103700858B
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- sodium
- perfluorocarbon
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M6/00—Primary cells; Manufacture thereof
- H01M6/14—Cells with non-aqueous electrolyte
- H01M6/16—Cells with non-aqueous electrolyte with organic electrolyte
- H01M6/162—Cells with non-aqueous electrolyte with organic electrolyte characterised by the electrolyte
- H01M6/164—Cells with non-aqueous electrolyte with organic electrolyte characterised by the electrolyte by the solvent
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- 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
- H01M4/381—Alkaline or alkaline earth metals elements
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- 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
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/5835—Comprising fluorine or fluoride salts
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M6/00—Primary cells; Manufacture thereof
- H01M6/14—Cells with non-aqueous electrolyte
- H01M6/16—Cells with non-aqueous electrolyte with organic electrolyte
- H01M6/162—Cells with non-aqueous electrolyte with organic electrolyte characterised by the electrolyte
- H01M6/168—Cells with non-aqueous electrolyte with organic electrolyte characterised by the electrolyte by additives
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- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
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- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
- Primary Cells (AREA)
Abstract
Sodium-perfluorocarbon one-shot battery, relates to a kind of sode cell.Being provided with positive pole, negative pole, barrier film and electrolyte, described positive pole adopts perfluorocarbon as active substance, and the main body of described perfluorocarbon is (CFx), x=0.2～1.2, in described active substance, perfluorocarbon content is 20%～100% by mass percentage；Described electrolyte is made up of solvent, electrolyte and additive.By business perfluorocarbon, as the subject active of sodium-perfluorocarbon one-shot battery positive pole including fluorographite, fluorizated petroleum coke, carbon fluoride nano-tube, fluorinated carbon fiber, fluorinated graphene etc.；With sodium metal for negative pole；Forming galvanic element system containing sodium salt electrolyte for electrolyte and barrier film with what organic solution was solvent, discharge with constant current density 20mA/g, its specific discharge capacity can reach more than 800mAh/g.There is the features such as discharge capacity height, discharge potential be steady and environmentally friendly.
Description
Technical field
The present invention relates to a kind of sode cell, especially relate to a kind of sodium-perfluorocarbon one-shot battery being positive pole with perfluorocarbon.
Background technology
Along with domestic economy is fast-developing, energy demand quickly increases, and energy problem is increasingly subject to people and pays close attention to.For a long time, traditional fossil energy shortage and greenhouse gas emission become one of human society future development main problem needing solution.Electrochemical power source, due to its performance got by oneself and the feature such as environmentally friendly, becomes one of society main path solving energy problem.Therefore, research and development have high-energy-density, high-specific-power, the novel battery of high security and critical material, it has also become the common recognition of countries in the world development.
Sodium metal is as the be only second to lithium second light metallic element, and it is in the abundance of the earth up to 2.3%～2.8%, and for 4～5 orders of magnitude of lithium metal, sode cell has great potential and the advantage of commercialization and sustainable use.Sode cell mainly includes the sodium-sulfur battery using sodium metal as negative pole, sodium-nickel chloride battery and sodium-air battery, and with sodium ion secondary battery that material with carbon element is negative pole.And about sodium-perfluorocarbon battery, report without correlational study.
Fluorinated carbon material is functional material between a kind of advanced carbon-coating that carbon and fluorine gas at high temperature direct reaction generate, and having surface can the physical and chemical performance of low and electroactive high a series of uniquenesses with interlayer.Perfluorocarbon is taken as excellent kollag and high-performance battery cathode material uses.Wherein, it is used primarily in lithium battery anode as battery cathode material, becomes battery with non-water system electrolyte combination.The Theoretical Mass specific energy of the lithium fluorocarbon battery formed is about 2180Wh/kg, is the highest in solid positive pole system, has caused electrochemistry scholar's extensive concern and research.Due to the physical and chemical performance that fluorinated carbon material is unique, forming widely studied and commercial production in states such as Japan and the United States as the fine functional material of high-tech, exploitation and study on the modification to fluorinated carbon material are also goed deep into gradually.Wherein, US Patent No. 4,770,959 in 1986 discloses lithium-perfluorocarbon battery；US Patent No. 5,106,606 discloses the study on the modification of fluorinated carbon fibre；US Patent No. 7,794,880B2 discloses the fluoride preparation technology of nano lamellar material with carbon element；Chinese patent CN102361084A openly adopts the mixture of fluorographite and carbon fluoride nano-tube as a kind of anode material of lithium battery.And about the fluorinated carbon material utilization in sode cell field, without relevant report.
Summary of the invention
It is an object of the invention to provide a kind of sodium-perfluorocarbon one-shot battery.
The present invention is provided with positive pole, negative pole, barrier film and electrolyte, and described positive pole adopts perfluorocarbon as active substance, and the main body of described perfluorocarbon is (CFx), x=0.2～1.2, in described active substance, perfluorocarbon content is 20%～100% by mass percentage；Described electrolyte is made up of solvent, electrolyte and additive.
Described fluorinated carbon material is the fluorinated carbon material obtained after perfluorinated by graphite, petroleum coke, CNT, carbon fiber or Graphene, or fluorinated carbon material prepared by other method.
Described negative pole can adopt at least one element and Na that sodium metal or sodium alloy, described sodium alloy be selected from Pb, Sn, Bi, Ga, Ce, Si.
Described solvent can adopt at least one that organic solvent, described organic solvent are selected from ethylene carbonate (EC), Allyl carbonate (PC), diethyl carbonate (DEC), 1,2-dimethoxy-ethane (DME), oxolane (THF) etc..
Described electrolyte can adopt sodium salt electrolyte, and described sodium salt electrolyte is selected from sodium hexafluoro phosphate (NaPF6), sodium perchlorate (NaClO4), sodium terachloroaluminate (NaAlCl4), tetrachloro sodium ferrite (NaFeCl4), sodium tetrafluoroborate (NaBF4), sodium nitrate (NaNO3), four sodium chloroborate (NaBCl4), hexafluoroarsenate sodium (NaAsF6) etc. at least one, electrolytical molar concentration can be 0.1～2mol/L.
Described additive can adopt at least one in vinylene carbonate (VC), vinylethylene carbonate (VEC), fluorinated ethylene carbonate (FEC) and other fluorinated solvents etc.；The percent by volume of described additive and organic solvent can be 0.2%～10%.
Described barrier film can adopt PP barrier film, PE barrier film, or PP/PE/PP composite membrane etc..
The present invention is by business perfluorocarbon, as the subject active of sodium-perfluorocarbon one-shot battery positive pole including fluorographite, fluorizated petroleum coke, carbon fluoride nano-tube, fluorinated carbon fiber, fluorinated graphene etc.；With sodium metal for negative pole；Galvanic element system is formed containing sodium salt electrolyte for electrolyte and barrier film with what organic solution was solvent.
Sodium-perfluorocarbon the one-shot battery using the present invention to prepare, discharges with constant current density 20mA/g, and its specific discharge capacity can reach more than 800mAh/g.The present invention has the features such as discharge capacity height, discharge potential be steady and environmentally friendly.
Accompanying drawing explanation
Fig. 1 is sodium of the present invention-perfluorocarbon one-shot battery structural representation.In FIG, respectively it is labeled as: 1, positive pole；2, negative pole；3, barrier film；4, electrolyte.
Fig. 2 is that the present invention adopts fluorinated carbon fiber (F/C=0.75) to prepare the constant current discharge curve of sode cell for positive pole.
Fig. 3 is that the present invention adopts fluorographite (F/C=0.75) to prepare the constant current discharge curve of sode cell for positive pole.
Fig. 4 is that the present invention adopts fluorographite (F/C=0.95) to prepare the constant current discharge curve of sode cell for positive pole.
Fig. 5 is that the present invention adopts fluorographite (F/C=1.05) to prepare the constant current discharge curve of sode cell for positive pole.
Fig. 6 is that the present invention adopts fluoride multi-walled carbon nano-tubes (F/C=0.75) to prepare the constant current discharge curve of sode cell for positive pole.
In Fig. 2～6, abscissa is specific capacity (Specificcapacity/mAhg-1), vertical coordinate is current potential Potential, V (vs.Na+/Na)。
Detailed description of the invention
Following example will the invention will be further described in conjunction with accompanying drawing.
Embodiment 1
Adopting preparation 2025 button sode cells that sodium of the present invention-perfluorocarbon one-shot battery carries out electrochemical property test, positive pole perfluorocarbon electrode is prepared by adopting coating method.Comprise the concrete steps that perfluorocarbon positive electrode in mass ratio: acetylene black: binding agent=80: 10: 10, perfluorocarbon, acetylene black and binding agent ball milling are mixed, is coated on the aluminium foil processed, in 120 DEG C of drying, compressing under 20MPa.Obtain sode cell positive pole.
Embodiment 2
Adopting the perfluorocarbon electrode prepared by embodiment 1 is positive pole, and sodium metal is negative pole, and PP/PE/PP composite membrane Cellgard2400 is barrier film, 1mol/LNaClO4Allyl carbonate (PC) solution be electrolyte, be assembled into 2025 button cells.Sode cell structural principle is as shown in Figure 1.LAND battery test system (Wuhan Land Electronic Co., Ltd.) carries out constant current electrochemical property test.Electric discharge is 1.5V(vs.Na by current potential+/ Na).
Embodiment 3
With fluorinated carbon fiber (F/C=0.75) for positive active material, prepare sode cell positive pole with reference to embodiment 1.Sode cell preparation and electrochemical property test is carried out with reference to embodiment 2.Test result is as shown in Figure 2.
Embodiment 4
With fluorographite (F/C=0.75) for positive active material, prepare sode cell positive pole with reference to embodiment 1.Sode cell preparation and electrochemical property test is carried out with reference to embodiment 2.Test result is as shown in Figure 3.
Embodiment 5
With fluorographite (F/C=0.95) for positive active material, prepare sode cell positive pole with reference to embodiment 1.Sode cell preparation and electrochemical property test is carried out with reference to embodiment 2.Test result is as shown in Figure 4.
Embodiment 6
With fluorographite (F/C=1.05) for positive active material, prepare sode cell positive pole with reference to embodiment 1.Sode cell preparation and electrochemical property test is carried out with reference to embodiment 2.Test result is as shown in Figure 5.
Embodiment 7
With fluoride multi-walled carbon nano-tubes (F/C=0.75) for positive active material, prepare sode cell positive pole with reference to embodiment 1.Sode cell preparation and electrochemical property test is carried out with reference to embodiment 2.Test result is as shown in Figure 6.
Embodiment 8
With fluorinated carbon fiber (F/C=0.75) for positive active material, prepare sode cell positive pole with reference to embodiment 1.With the electrode of above-mentioned preparation for positive pole, sodium metal is negative pole, and PP/PE/PP composite membrane Cellgard2400 is barrier film, 1mol/LNaClO4PC+FEC(98: 2v/v) solution is electrolyte, is assembled into 2025 button sode cells.Electrochemical property test is carried out with reference to embodiment 2.
Claims (4)
1. sodium-perfluorocarbon one-shot battery, it is characterised in that be provided with positive pole, negative pole, barrier film and electrolyte, described positive pole adopts perfluorocarbon as active substance, and the main body of described perfluorocarbon is CFx, x=0.2 ~ 1.2, in described active substance, perfluorocarbon content is 20%～100% by mass percentage；Described electrolyte is made up of solvent, electrolyte and additive；
Described electrolyte adopts sodium salt electrolyte；
Described sodium salt electrolyte at least one in sodium hexafluoro phosphate, sodium perchlorate, sodium terachloroaluminate, tetrachloro sodium ferrite, sodium tetrafluoroborate, sodium nitrate, four sodium chloroborates, hexafluoroarsenate sodium, electrolytical molar concentration is 0.1～2mol/L；
Described additive adopts at least one in vinylene carbonate, vinylethylene carbonate, fluorinated ethylene carbonate；The percent by volume of described additive and organic solvent is 0.2%～10%；
Described fluorinated carbon material is the fluorinated carbon material obtained after perfluorinated by graphite, petroleum coke, CNT, carbon fiber or Graphene；
Described negative pole adopts sodium metal or sodium alloy；
Described sodium alloy is selected from least one element in Pb, Sn, Bi, Ga, Ce, Si and Na.
2. sodium-perfluorocarbon one-shot battery as claimed in claim 1, it is characterised in that described solvent adopts organic solvent.
3. sodium-perfluorocarbon one-shot battery as claimed in claim 2, it is characterised in that described organic solvent at least one in ethylene carbonate, Allyl carbonate, diethyl carbonate, 1,2-dimethoxy-ethane, oxolane.
4. sodium-perfluorocarbon one-shot battery as claimed in claim 1, it is characterised in that described barrier film adopts PP barrier film, PE barrier film, or PP/PE/PP composite membrane.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201410006534.5A CN103700858B (en) | 2014-01-07 | 2014-01-07 | Sodium-perfluorocarbon one-shot battery |
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| CN201410006534.5A CN103700858B (en) | 2014-01-07 | 2014-01-07 | Sodium-perfluorocarbon one-shot battery |
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| CN103700858A CN103700858A (en) | 2014-04-02 |
| CN103700858B true CN103700858B (en) | 2016-07-06 |
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105655587B (en) * | 2014-11-10 | 2019-09-20 | 中国电子科技集团公司第十八研究所 | Lithium primary battery CFx positive electrode surface coating method |
| CN104577196B (en) * | 2015-01-09 | 2017-03-08 | 厦门大学 | High voltage sodium perfluorocarbon secondary cell |
| CN106229506B (en) * | 2016-08-17 | 2018-09-18 | 天津大学 | A method of fluorocarbons discharge voltage is regulated and controled by graphene planes curvature |
| CN107611446A (en) * | 2017-09-20 | 2018-01-19 | 厦门稀土材料研究所 | A kind of liberation of hydrogen inhibitor, preparation method and applications |
| CN112670528B (en) * | 2020-12-23 | 2023-07-25 | 湘潭大学 | Preparation method of high-rate primary alkali metal battery |
| CN116259827B (en) * | 2021-12-10 | 2024-05-24 | 张家港市国泰华荣化工新材料有限公司 | Sodium-manganese primary cell |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4327166A (en) * | 1980-09-29 | 1982-04-27 | Union Carbide Corporation | Nonaqueous cell having a MNO2 /poly-carbon fluoride cathode |
| CN102754249A (en) * | 2009-12-04 | 2012-10-24 | 伊格皮切尔科技有限责任公司 | Non-aqueous cell having a mixture of fluorinated carbon cathode materials |
| CN103022455A (en) * | 2011-09-08 | 2013-04-03 | 伊格皮切尔科技有限责任公司 | High rate and energy cathode material for lithium batteries |
| CN103441302A (en) * | 2013-08-23 | 2013-12-11 | 宁德时代新能源科技有限公司 | Lithium ion battery and electrolyte thereof |
-
2014
- 2014-01-07 CN CN201410006534.5A patent/CN103700858B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4327166A (en) * | 1980-09-29 | 1982-04-27 | Union Carbide Corporation | Nonaqueous cell having a MNO2 /poly-carbon fluoride cathode |
| CN102754249A (en) * | 2009-12-04 | 2012-10-24 | 伊格皮切尔科技有限责任公司 | Non-aqueous cell having a mixture of fluorinated carbon cathode materials |
| CN103022455A (en) * | 2011-09-08 | 2013-04-03 | 伊格皮切尔科技有限责任公司 | High rate and energy cathode material for lithium batteries |
| CN103441302A (en) * | 2013-08-23 | 2013-12-11 | 宁德时代新能源科技有限公司 | Lithium ion battery and electrolyte thereof |
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