CN106384674A - Aqueous rechargeable sodium-ion capacitor battery based on titanium phosphorus oxide cathode material - Google Patents
Aqueous rechargeable sodium-ion capacitor battery based on titanium phosphorus oxide cathode material Download PDFInfo
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- CN106384674A CN106384674A CN201610938549.4A CN201610938549A CN106384674A CN 106384674 A CN106384674 A CN 106384674A CN 201610938549 A CN201610938549 A CN 201610938549A CN 106384674 A CN106384674 A CN 106384674A
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- Prior art keywords
- sodium
- titanium
- phosphorous oxides
- ion
- water system
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- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 61
- 239000003990 capacitor Substances 0.000 title claims abstract description 40
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 27
- HLYZSYKQHVOJQU-UHFFFAOYSA-N [P]=O.[Ti] Chemical compound [P]=O.[Ti] HLYZSYKQHVOJQU-UHFFFAOYSA-N 0.000 title abstract 6
- 239000010406 cathode material Substances 0.000 title abstract 4
- 239000000463 material Substances 0.000 claims abstract description 45
- IKULXUCKGDPJMZ-UHFFFAOYSA-N sodium manganese(2+) oxygen(2-) Chemical compound [O-2].[Mn+2].[Na+] IKULXUCKGDPJMZ-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000006258 conductive agent Substances 0.000 claims abstract description 25
- 239000003792 electrolyte Substances 0.000 claims abstract description 19
- 238000002360 preparation method Methods 0.000 claims abstract description 19
- 238000001354 calcination Methods 0.000 claims abstract description 16
- 229910017053 inorganic salt Inorganic materials 0.000 claims abstract description 14
- 238000000227 grinding Methods 0.000 claims abstract description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 70
- 239000010936 titanium Substances 0.000 claims description 70
- 229910052719 titanium Inorganic materials 0.000 claims description 70
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 claims description 60
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 60
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 32
- 239000011734 sodium Substances 0.000 claims description 29
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 28
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 27
- 229910052708 sodium Inorganic materials 0.000 claims description 27
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 25
- 239000000203 mixture Substances 0.000 claims description 19
- 239000011230 binding agent Substances 0.000 claims description 18
- 230000004888 barrier function Effects 0.000 claims description 17
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 17
- 239000008367 deionised water Substances 0.000 claims description 16
- 229910021641 deionized water Inorganic materials 0.000 claims description 16
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 16
- 238000005406 washing Methods 0.000 claims description 15
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 14
- 239000012266 salt solution Substances 0.000 claims description 13
- 239000011572 manganese Substances 0.000 claims description 12
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 10
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 10
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 claims description 10
- 229910052748 manganese Inorganic materials 0.000 claims description 10
- 229910052698 phosphorus Inorganic materials 0.000 claims description 10
- 239000011574 phosphorus Substances 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 8
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- 229910000348 titanium sulfate Inorganic materials 0.000 claims description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 229910002804 graphite Inorganic materials 0.000 claims description 6
- 239000010439 graphite Substances 0.000 claims description 6
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 6
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 5
- 229920001328 Polyvinylidene chloride Polymers 0.000 claims description 5
- 229910052744 lithium Inorganic materials 0.000 claims description 5
- 229950000845 politef Drugs 0.000 claims description 5
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 5
- 239000005033 polyvinylidene chloride Substances 0.000 claims description 5
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 4
- 239000006229 carbon black Substances 0.000 claims description 4
- 239000002134 carbon nanofiber Substances 0.000 claims description 4
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 4
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 4
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 229910021389 graphene Inorganic materials 0.000 claims description 4
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 4
- 239000001488 sodium phosphate Substances 0.000 claims description 4
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 4
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 3
- 229910021502 aluminium hydroxide Inorganic materials 0.000 claims description 3
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- PTVDYARBVCBHSL-UHFFFAOYSA-N copper;hydrate Chemical compound O.[Cu] PTVDYARBVCBHSL-UHFFFAOYSA-N 0.000 claims description 3
- 150000002500 ions Chemical class 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 3
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 3
- 239000012982 microporous membrane Substances 0.000 claims description 3
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 3
- LLYXJBROWQDVMI-UHFFFAOYSA-N 2-chloro-4-nitrotoluene Chemical compound CC1=CC=C([N+]([O-])=O)C=C1Cl LLYXJBROWQDVMI-UHFFFAOYSA-N 0.000 claims description 2
- BZSXEZOLBIJVQK-UHFFFAOYSA-N 2-methylsulfonylbenzoic acid Chemical compound CS(=O)(=O)C1=CC=CC=C1C(O)=O BZSXEZOLBIJVQK-UHFFFAOYSA-N 0.000 claims description 2
- 229910014485 Na0.44MnO2 Inorganic materials 0.000 claims description 2
- 239000004743 Polypropylene Substances 0.000 claims description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 2
- 239000002322 conducting polymer Substances 0.000 claims description 2
- 229920001940 conductive polymer Polymers 0.000 claims description 2
- 239000003365 glass fiber Substances 0.000 claims description 2
- 239000004745 nonwoven fabric Substances 0.000 claims description 2
- 229920000573 polyethylene Polymers 0.000 claims description 2
- -1 polypropylene Polymers 0.000 claims description 2
- 229920001155 polypropylene Polymers 0.000 claims description 2
- 239000004317 sodium nitrate Substances 0.000 claims description 2
- 235000010344 sodium nitrate Nutrition 0.000 claims description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 2
- 235000011152 sodium sulphate Nutrition 0.000 claims description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims 2
- 235000017550 sodium carbonate Nutrition 0.000 claims 1
- 239000011780 sodium chloride Substances 0.000 claims 1
- 235000002639 sodium chloride Nutrition 0.000 claims 1
- 235000011121 sodium hydroxide Nutrition 0.000 claims 1
- 239000000853 adhesive Substances 0.000 abstract description 6
- 230000001070 adhesive effect Effects 0.000 abstract description 6
- 239000002253 acid Substances 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 3
- 239000011149 active material Substances 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- OJIJEKBXJYRIBZ-UHFFFAOYSA-N cadmium nickel Chemical compound [Ni].[Cd] OJIJEKBXJYRIBZ-UHFFFAOYSA-N 0.000 abstract 1
- 238000002156 mixing Methods 0.000 abstract 1
- 238000009475 tablet pressing Methods 0.000 abstract 1
- 238000000034 method Methods 0.000 description 14
- 230000007613 environmental effect Effects 0.000 description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 229910001416 lithium ion Inorganic materials 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000012298 atmosphere Substances 0.000 description 3
- 239000011258 core-shell material Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000007774 positive electrode material Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 239000002228 NASICON Substances 0.000 description 2
- 229910018502 Ni—H Inorganic materials 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 229910052793 cadmium Inorganic materials 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000012983 electrochemical energy storage Methods 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910018095 Ni-MH Inorganic materials 0.000 description 1
- 229910018477 Ni—MH Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- RTTUXDWYMFNHKW-UHFFFAOYSA-N [Mn](=O)(=O)([O-])[O-].[Na+].[Co+2].[Ni+2] Chemical compound [Mn](=O)(=O)([O-])[O-].[Na+].[Co+2].[Ni+2] RTTUXDWYMFNHKW-UHFFFAOYSA-N 0.000 description 1
- BNOODXBBXFZASF-UHFFFAOYSA-N [Na].[S] Chemical compound [Na].[S] BNOODXBBXFZASF-UHFFFAOYSA-N 0.000 description 1
- DMPVSURQCULMSQ-UHFFFAOYSA-N [O].[Mn].[Na] Chemical compound [O].[Mn].[Na] DMPVSURQCULMSQ-UHFFFAOYSA-N 0.000 description 1
- QGSHSAIWXUKKBE-UHFFFAOYSA-N [O].[P].[Ti] Chemical compound [O].[P].[Ti] QGSHSAIWXUKKBE-UHFFFAOYSA-N 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 229910052979 sodium sulfide Inorganic materials 0.000 description 1
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 238000003836 solid-state method Methods 0.000 description 1
- 238000010671 solid-state reaction Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/04—Hybrid capacitors
- H01G11/06—Hybrid capacitors with one of the electrodes allowing ions to be reversibly doped thereinto, e.g. lithium ion capacitors [LIC]
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/46—Metal oxides
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/54—Electrolytes
- H01G11/58—Liquid electrolytes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/54—Electrolytes
- H01G11/58—Liquid electrolytes
- H01G11/62—Liquid electrolytes characterised by the solute, e.g. salts, anions or cations therein
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
-
- 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
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention provides an aqueous rechargeable sodium-ion capacitor battery based on a titanium phosphorus oxide cathode material. The aqueous rechargeable sodium-ion capacitor battery based on a titanium phosphorus oxide cathode material comprises a positive electrode, a negative electrode, a separator and electrolyte. The positive electrode comprises a sodium manganese oxide, conductive agent and adhesive. The negative electrode comprises a titanium phosphorus oxide, conductive agent and adhesive. The electrolyte is inorganic salt water-soluble solution containing sodium ions. The sodium manganese oxide and the titanium phosphorus oxide are obtained by the steps of raw material mixing, grinding, tablet pressing and calcining. The aqueous rechargeable sodium-ion capacitor battery based on a titanium phosphorus oxide cathode material has higher energy efficiency, higher power density, a longer cycle life and higher utilization rate of active materials than lead-acid batteries, and is cheaper, safer and more environment-friendly than cadmium-nickel batteries and hydrogen-nickel batteries. The preparation process is simple, and the battery can be prepared directly in the air. The battery has low requirement for the environment, has a wide range of material sources, is low in cost, and is suitable for industrialized mass production.
Description
Technical field
The invention belongs to battery material technical field is and in particular to a kind of water system based on titanium phosphorous oxides negative material can
Fill sodium ion capacitor batteries.
Background technology
The energy is formed into the material base of whole human civilization progress, with regenerative resource and renewable energy technologies
Develop rapidly, wind energy, solar energy, tide energy and geothermal energy etc. belong to renewable and clean energy resource, by these renewable cleaning energy
Source efficient Portable safety storage becomes the emphasis of research.Electrochemical energy storage is a kind of efficiency high, small investment, uses safety, uses
The features such as flexible, electrochemical energy storage is divided into sodium-sulphur battery, flow battery, Ni-MH battery and lithium ion battery.Wherein lithium ion
Battery has that energy density is big, has extended cycle life, running voltage height, memory-less effect, little, the operating temperature range width of self discharge etc.
Advantage, is gradually applied to electric automobile, the safety problem of lithium ion battery, life problems and Cost Problems with lithium ion battery
Gradually highlight, therefore, be badly in need of developing a kind of excellent energy-storage battery new system of comprehensive effectiveness.
For comparing lithium resource, sodium reserves very abundant, and also widely distributed, refine simple, and sodium and lithium have phase
As physicochemical properties, the operation principle of sodium-ion battery is also similar with lithium ion, and discharge and recharge is reversible.Chinese patent CN
A kind of water system sodium ion capacitor batteries disclosed in 203839466U, this battery includes two nickel foil electrodes, Na super ionic conductor electrode
Material layer, absorbent charcoal material layer, barrier film and sodium salt organic electrolyte, using the sodium ion of Na super ionic conductor electrode material layer
Deintercalation, realizes the charge and discharge process of electrode.A kind of sodium-ion battery negative pole material disclosed in Chinese patent CN 102916186B
The preparation method of material and negative pole and sodium-ion battery, the negative material of this sodium-ion battery is by sodium sulfide, simple substance niobium and simple substance
Sulfur, as raw material, is prepared using high temperature solid-state method and is formed sulfide negative material, then be compounded to form sodium with acetylene black and binding agent
Ion battery negative pole, cell positive material is cobalt acid sodium, nickel acid sodium, nickel cobalt sodium manganate etc., last with barrier film and sodium salt non-aqueous
Solvent is compounded to form battery material, and the battery material of preparation has good charge/discharge capacity and cycle performance.But, current sodium
Ion capacitance battery adopt raw material relatively costly, preparation technology is complex, and environmental requirement is higher.
, using titanium phosphorous oxides as negative active core-shell material, sodium manganese oxide is as positive-active material for applicant of the present invention
Material, both can calcine under air atmosphere, and the assembling of battery can also be carried out under air atmosphere, preparation technology letter
Single, and low cost, it is suitable for industrialized production.
Content of the invention
The technical problem to be solved in the present invention be provide a kind of based on the water system of titanium phosphorous oxides negative material can fill sodium from
Sub- capacitor batteries, using titanium phosphorous oxides as negative active core-shell material, sodium manganese oxide is as positive electrode active materials, additional conductive agent
And adhesive, prepare formation negative pole and positive pole respectively, then form water system Na ion chargeable electric capacity electricity with barrier film and electrolyte combination
Pond.Preparation process of the present invention is simple, low to environmental requirement, preparation battery than lead-acid battery have higher energy efficiency,
Power density, cycle life and active material utilization etc., and ratio ickel-cadmium cell and Ni-H cell low cost, safety and environmental protection.
For solving above-mentioned technical problem, the technical scheme is that：
A kind of water system Na ion chargeable capacitor batteries based on titanium phosphorous oxides negative material, described based on titanium phosphorous oxides
The water system Na ion chargeable capacitor batteries of negative material include positive pole, negative pole, barrier film and electrolyte, and described positive pole includes sodium manganese oxygen
Compound, conductive agent and binding agent, described negative pole includes titanium phosphorous oxides, conductive agent and binding agent, and described sodium manganese oxide is
Na0.44MnO2Or Na0.44Mn1-yMyO2, 0≤y≤0.1, described M is one of Al, Li, Fe, Co, Ni, Cu or two kinds,
Described titanium phosphorous oxides is (TiO)aPbOc, c=a+2.5b, 0≤a≤3,0≤b≤3,0≤c≤12, described conductive agent is porous
One of activated carbon, mesoporous carbon, white carbon black, graphite, CNT, Graphene, carbon nano-fiber or expanded graphite.
Preferred as technique scheme, described conductive agent can also be conducting polymer.
Preferred as technique scheme, described binding agent be politef, polyvinylidene chloride, polrvinyl chloride,
One of polyvinyl alcohol, carboxymethyl cellulose-based sodium.
Preferred as technique scheme, described electrolyte is the inorganic salt solution containing sodium ion, described containing sodium from
In the inorganic salt solution of son, the concentration of sodium ion is 0.5-10mol/L.
Preferred as technique scheme, the described inorganic salt solution containing sodium ion is sodium sulfate, sodium nitrate, chlorination
One or more of sodium, sodium hydroxide, sodium carbonate, sodium phosphate, dibastic sodium phosphate, disodium hydrogen phosphate, sodium chlorate.
Preferred as technique scheme, described barrier film between positive pole and negative pole, described barrier film be polypropylene screen,
One of non-woven fabrics, polrvinyl chloride microporous membrane, polyethene microporous membrane, glass fibre.
Preferred as technique scheme, the described water system Na ion chargeable electric capacity based on titanium phosphorous oxides negative material
Battery preparation method, comprises the following steps：
(1) with manganese dioxide as manganese source, sodium carbonate is sodium source, lithium carbonate, aluminium hydroxide, ferric nitrate, chromic nitrate, nickel nitrate
Or Copper hydrate be the 3rd source, by three's mixed grinding, tabletting, at 500 DEG C calcining 5h, grind again, tabletting, in 850-
Calcine 12h, then deionized water and absolute ethanol washing successively at 900 DEG C, dry at 60 DEG C, obtain sodium manganese oxide；
(2) sodium manganese oxide prepared by step (1) is added in dehydrated alcohol, mix homogeneously, add conductive agent and glue
Knot agent, mixes, tabletting, dries, obtains positive pole；
(3) with titanium sulfate as titanium source, disodium hydrogen phosphate as phosphorus source, after both are mixed, add sodium carbonate, heating in water bath is extremely
Solvent volatilization is complete, and deionized water and absolute ethanol washing successively is dried, calcining, obtains titanium phosphorous oxides；
(4) titanium phosphorous oxides prepared by step (3) is added in dehydrated alcohol, mix homogeneously, add conductive agent and glue
Knot agent, mixes, tabletting, dries, obtains negative pole；
(5) negative pole and electrolyte assembling prepared by the positive pole prepared step (2) successively, barrier film, step (4), form base
Water system Na ion chargeable capacitor batteries in titanium phosphorous oxides negative material.
Preferred as technique scheme, the mol ratio of the manganese source, sodium source and the 3rd source of described step (1) is 0.22-
0.44:0.9-1:0-0.1.
Preferred as technique scheme, the titanium source of described step (3) and the mol ratio of phosphorus source are 1:1-2.
Preferred as technique scheme, in sodium manganese oxide and negative pole in the positive pole of described step (5) titanium phosphorus oxygen
The mass ratio of compound is 1.5-2.5:1.
Compared with prior art, the invention has the advantages that：
(1) the water system Na ion chargeable capacitor batteries of present invention preparation, using titanium phosphorous oxides as negative active core-shell material, are incited somebody to action
, as positive electrode active materials, both material structures are stable for sodium manganese oxide, compared with traditional carbons activated carbon, titanium phosphorous oxides
With sodium manganese oxide, there is more preferable energy efficiency and specific discharge capacity, good cycling stability, and word solid state reaction legal system
Standby positive pole and negative material, preparation method is simple, wide material sources, and cheap, environmental protection, advantageously in batch production scale
Produce.
(2) the water system Na ion chargeable capacitor batteries of present invention preparation can be prepared under air atmosphere and assemble, technique
Simply, environment is loose, and using inorganic salt solution as electrolyte, more safety and environmental protection, with low cost, and present invention preparation
Positive electrode in also contain Al, Li, Fe, Co, Ni, Cu ion, increased the specific surface area of sodium manganese oxide, improve activity
The specific capacity of positive electrode and energy density.
(3), in charging process, sodium ion is from positive electrode for the water system Na ion chargeable capacitor batteries of present invention preparation
Abjection, is adsorbed on the surface of negative material by electrolyte, and electric charge forms the double electricity of sodium ion between negative terminal surface and electrolyte
Layer, in putting point process, sodium ion parses from negative terminal surface, is entered in positive electrode by electrolyte, realizes discharge and recharge.
(4) the water system Na ion chargeable capacitor batteries of present invention preparation are compared with lead-acid battery, capacitor batteries can dose-effect
Rate is high, specific energy is high, power density is high, have extended cycle life, good rate capability, compared with ickel-cadmium cell and Ni-H cell, electric capacity
The overall cost of battery is low, safety and environmental protection, and the water system Na ion chargeable capacitor batteries of therefore present invention preparation can be applicable to advise greatly
The fields such as mould energy transfer medium system, battery car use and Aero-Space.
Specific embodiment
To describe the present invention, the illustrative examples of the here present invention and explanation below in conjunction with specific embodiment in detail
It is used for explaining the present invention, but not as a limitation of the invention.
Embodiment 1：
(1) with manganese dioxide as manganese source, sodium carbonate is sodium source, with mol ratio for 0.22:1, by three's mixed grinding, pressure
Piece, at 500 DEG C calcining 5h, grind again, tabletting, calcine 12h, then deionized water and dehydrated alcohol successively at 900 DEG C
Washing, dries at 60 DEG C, obtains sodium manganese oxide.
(2) by weight, 80 parts of sodium manganese oxide is added in dehydrated alcohol, mix homogeneously, add 16 parts
The politef binding agent of porous activated carbon conductive agent and 4 parts, mixes, tabletting, dries, obtains positive pole；
(3) with titanium sulfate as titanium source, disodium hydrogen phosphate as phosphorus source, with mol ratio for 1:1, after both are mixed, add carbon
Sour sodium, at 60 DEG C, heating in water bath is complete to solvent volatilization, and deionized water and absolute ethanol washing successively is dried, at 700 DEG C
Lower calcining 8h, obtains titanium phosphorous oxides.
(4) by weight, 80 parts of titanium phosphorous oxides is added in dehydrated alcohol, mix homogeneously, add 16 parts
The politef binding agent of porous activated carbon conductive agent and 4 parts, mixes, tabletting, dries, obtains negative pole.
(5) successively by positive pole, barrier film, negative pole and concentration be 0.5mol/L the inorganic salt solution electrolyte containing sodium ion
Assembling, forms the water system Na ion chargeable capacitor batteries based on titanium phosphorous oxides negative material, wherein sodium manganese oxide in positive pole
Mass ratio with the titanium phosphorous oxides in negative pole is 1.5:1.
Embodiment 2：
(1) with manganese dioxide as manganese source, sodium carbonate is sodium source, and lithium carbonate is the 3rd source, with mol ratio for 0.44:0.9:
0.1, by three's mixed grinding, tabletting, at 500 DEG C calcining 5h, grind again, tabletting, at 850 DEG C calcine 12h, then successively
Deionized water and absolute ethanol washing, dry at 60 DEG C, obtain sodium manganese oxide.
(2) by weight, 80 parts of sodium manganese oxide is added in dehydrated alcohol, mix homogeneously, add 16 parts
The polyvinylidene chloride binding agent of mesoporous carbonaceous conductive agent and 4 parts, mixes, tabletting, dries, obtains positive pole；
(3) with titanium sulfate as titanium source, disodium hydrogen phosphate as phosphorus source, with mol ratio for 1:2, after both are mixed, add carbon
Sour sodium, at 70 DEG C, heating in water bath is complete to solvent volatilization, and deionized water and absolute ethanol washing successively is dried, at 700 DEG C
Lower calcining 8h, obtains titanium phosphorous oxides.
(4) by weight, 80 parts of titanium phosphorous oxides is added in dehydrated alcohol, mix homogeneously, add 16 parts
The polyvinylidene chloride binding agent of mesoporous carbonaceous conductive agent and 4 parts, mixes, tabletting, dries, obtains negative pole.
(5) successively by positive pole, barrier film, negative pole and concentration be 10mol/L the inorganic salt solution electrolyte containing sodium ion
Assembling, forms the water system Na ion chargeable capacitor batteries based on titanium phosphorous oxides negative material, wherein sodium manganese oxide in positive pole
Mass ratio with the titanium phosphorous oxides in negative pole is 2.5:1.
Embodiment 3：
(1) with manganese dioxide as manganese source, sodium carbonate is sodium source, and aluminium hydroxide is the 3rd source, with mol ratio for 0.22:
0.95:0.05, by three's mixed grinding, tabletting, at 500 DEG C calcining 5h, grind again, tabletting, at 900 DEG C calcine 12h, so
Deionized water and absolute ethanol washing successively afterwards, dries at 60 DEG C, obtains sodium manganese oxide.
(2) by weight, 80 parts of sodium manganese oxide is added in dehydrated alcohol, mix homogeneously, add 16 parts
The carboxymethyl cellulose-based sodium binding agent of carbon black conductive agent and 4 parts, mixes, tabletting, dries, obtains positive pole；
(3) with titanium sulfate as titanium source, disodium hydrogen phosphate as phosphorus source, with mol ratio for 1:1.5, after both are mixed, add
Sodium carbonate, at 65 DEG C, heating in water bath is complete to solvent volatilization, and deionized water and absolute ethanol washing successively is dried, 700
Calcine 8h at DEG C, obtain titanium phosphorous oxides.
(4) by weight, 80 parts of titanium phosphorous oxides is added in dehydrated alcohol, mix homogeneously, add 16 parts
The polyvinyl alcohol adhesive of graphite agent and 4 parts, mixes, tabletting, dries, obtains negative pole.
(5) successively by positive pole, barrier film, negative pole and concentration be 5mol/L the inorganic salt solution electrolyte group containing sodium ion
Dress, forms water system Na ion chargeable capacitor batteries based on titanium phosphorous oxides negative material, wherein in positive pole sodium manganese oxide with
The mass ratio of the titanium phosphorous oxides in negative pole is 2:1.
Embodiment 4：
(1) with manganese dioxide as manganese source, sodium carbonate is sodium source, and ferric nitrate is the 3rd source, with mol ratio for 0.44:0.9:
0.1, by three's mixed grinding, tabletting, at 500 DEG C calcining 5h, grind again, tabletting, at 900 DEG C calcine 12h, then successively
Deionized water and absolute ethanol washing, dry at 60 DEG C, obtain sodium manganese oxide.
(2) by weight, 80 parts of sodium manganese oxide is added in dehydrated alcohol, mix homogeneously, add 16 parts
The polyvinylidene chloride binding agent of graphene conductive agent and 4 parts, mixes, tabletting, dries, obtains positive pole；
(3) with titanium sulfate as titanium source, disodium hydrogen phosphate as phosphorus source, with mol ratio for 1:2, after both are mixed, add carbon
Sour sodium, at 70 DEG C, heating in water bath is complete to solvent volatilization, and deionized water and absolute ethanol washing successively is dried, at 700 DEG C
Lower calcining 8h, obtains titanium phosphorous oxides.
(4) by weight, 80 parts of titanium phosphorous oxides is added in dehydrated alcohol, mix homogeneously, add 16 parts
The polyvinyl alcohol adhesive of graphene conductive agent and 4 parts, mixes, tabletting, dries, obtains negative pole.
(5) successively by positive pole, barrier film, negative pole and concentration be 2mol/L the inorganic salt solution electrolyte group containing sodium ion
Dress, forms water system Na ion chargeable capacitor batteries based on titanium phosphorous oxides negative material, wherein in positive pole sodium manganese oxide with
The mass ratio of the titanium phosphorous oxides in negative pole is 1.5:1.
Embodiment 5：
(1) with manganese dioxide as manganese source, sodium carbonate is sodium source, and nickel nitrate or Copper hydrate are the 3rd source, with mol ratio
For 0.22:0.97:0.03, by three's mixed grinding, tabletting, at 500 DEG C calcining 5h, grind again, tabletting, forge at 900 DEG C
Burn 12h, then deionized water and absolute ethanol washing successively, dry at 60 DEG C, obtain sodium manganese oxide.
(2) by weight, 80 parts of sodium manganese oxide is added in dehydrated alcohol, mix homogeneously, add 16 parts
The politef binding agent of expanded graphite conductive agent and 4 parts, mixes, tabletting, dries, obtains positive pole；
(3) with titanium sulfate as titanium source, disodium hydrogen phosphate as phosphorus source, with mol ratio for 1:1.5, after both are mixed, add
Sodium carbonate, at 70 DEG C, heating in water bath is complete to solvent volatilization, and deionized water and absolute ethanol washing successively is dried, 700
Calcine 8h at DEG C, obtain titanium phosphorous oxides.
(4) by weight, 80 parts of titanium phosphorous oxides is added in dehydrated alcohol, mix homogeneously, add 16 parts
The carboxymethyl cellulose-based sodium binding agent of carbon black conductive agent and 4 parts, mixes, tabletting, dries, obtains negative pole.
(5) successively by positive pole, barrier film, negative pole and concentration be 6mol/L the inorganic salt solution electrolyte group containing sodium ion
Dress, forms water system Na ion chargeable capacitor batteries based on titanium phosphorous oxides negative material, wherein in positive pole sodium manganese oxide with
The mass ratio of the titanium phosphorous oxides in negative pole is 1.5:1.
Embodiment 6：
(1) with manganese dioxide as manganese source, sodium carbonate is sodium source, and chromic nitrate is the 3rd source, with mol ratio for 0.44:0.9:
0.1, by three's mixed grinding, tabletting, at 500 DEG C calcining 5h, grind again, tabletting, at 900 DEG C calcine 12h, then successively
Deionized water and absolute ethanol washing, dry at 60 DEG C, obtain sodium manganese oxide.
(2) by weight, 80 parts of sodium manganese oxide is added in dehydrated alcohol, mix homogeneously, add 16 parts
The polyvinyl alcohol adhesive of carbon nano-fiber conductive agent and 4 parts, mixes, tabletting, dries, obtains positive pole；
(3) with titanium sulfate as titanium source, disodium hydrogen phosphate as phosphorus source, with mol ratio for 1:1, after both are mixed, add carbon
Sour sodium, at 70 DEG C, heating in water bath is complete to solvent volatilization, and deionized water and absolute ethanol washing successively is dried, at 700 DEG C
Lower calcining 8h, obtains titanium phosphorous oxides.
(4) by weight, 80 parts of titanium phosphorous oxides is added in dehydrated alcohol, mix homogeneously, add 16 parts
The polyvinyl-chloride binders of carbon nano-fiber conductive agent and 4 parts, mix, tabletting, dry, obtain negative pole.
(5) successively by positive pole, barrier film, negative pole and concentration be 2mol/L the inorganic salt solution electrolyte group containing sodium ion
Dress, forms water system Na ion chargeable capacitor batteries based on titanium phosphorous oxides negative material, wherein in positive pole sodium manganese oxide with
The mass ratio of the titanium phosphorous oxides in negative pole is 1.5:1.
The capacitor batteries performance test methods of embodiment 1-6 preparation：In 100-2000mA g-1Electric current density, 0.01-
1.8V voltage range carries out charge-discharge test, after testing, the water system based on titanium phosphorous oxides negative material of embodiment 1-6 preparation
The result of the specific discharge capacity of Na ion chargeable capacitor batteries is as follows：
The putting of the water system Na ion chargeable capacitor batteries based on titanium phosphorous oxides negative material that charge and discharge cycles are 1000 times
The result of electric specific capacity, device energy density and coulombic efficiency conservation rate is as follows：
As seen from the above table, the water system Na ion chargeable capacitor batteries based on titanium phosphorous oxides negative material of present invention preparation
Specific discharge capacity is good, and after circulating 1000 times, specific discharge capacity improves and good stability, and device energy density and coulombic efficiency keep
Rate is good.
Above-described embodiment only principle of the illustrative present invention and its effect, not for the restriction present invention.Any ripe
The personage knowing this technology all can carry out modifications and changes without prejudice under the spirit and the scope of the present invention to above-described embodiment.Cause
This, those of ordinary skill in the art is complete with institute under technological thought without departing from disclosed spirit such as
All equivalent modifications becoming or change, must be covered by the claim of the present invention.
Claims (10)
1. a kind of water system Na ion chargeable capacitor batteries based on titanium phosphorous oxides negative material it is characterised in that：Described it is based on
The water system Na ion chargeable capacitor batteries of titanium phosphorous oxides negative material include positive pole, negative pole, barrier film and electrolyte, described positive pole
Including sodium manganese oxide, conductive agent and binding agent, described negative pole includes titanium phosphorous oxides, conductive agent and binding agent, described sodium manganese
Oxide is Na0.44MnO2Or Na0.44Mn1-yMyO2, 0≤y≤0.1, described M be one of Al, Li, Fe, Co, Ni, Cu or
Two kinds of person, described titanium phosphorous oxides is (TiO)aPbOc, c=a+2.5b, 0≤a≤3,0≤b≤3,0≤c≤12, described conduction
Agent is in porous activated carbon, mesoporous carbon, white carbon black, graphite, CNT, Graphene, carbon nano-fiber or expanded graphite
Kind.
2. a kind of water system Na ion chargeable capacitor batteries based on titanium phosphorous oxides negative material according to claim 1,
It is characterized in that：Described conductive agent can also be conducting polymer.
3. a kind of water system Na ion chargeable capacitor batteries based on titanium phosphorous oxides negative material according to claim 1,
It is characterized in that：Described binding agent is politef, polyvinylidene chloride, polrvinyl chloride, polyvinyl alcohol, carboxymethyl cellulose
One of base sodium.
4. a kind of water system Na ion chargeable capacitor batteries based on titanium phosphorous oxides negative material according to claim 1,
It is characterized in that：Described electrolyte is the inorganic salt solution containing sodium ion, sodium in the described inorganic salt solution containing sodium ion
The concentration of ion is 0.5-10mol/L.
5. a kind of water system Na ion chargeable capacitor batteries based on titanium phosphorous oxides negative material according to claim 4,
It is characterized in that：The described inorganic salt solution containing sodium ion be sodium sulfate, sodium nitrate, sodium chloride, sodium hydroxide, sodium carbonate,
One or more of sodium phosphate, dibastic sodium phosphate, disodium hydrogen phosphate, sodium chlorate.
6. a kind of water system Na ion chargeable capacitor batteries based on titanium phosphorous oxides negative material according to claim 1,
It is characterized in that：Between positive pole and negative pole, described barrier film is polypropylene screen, non-woven fabrics, polrvinyl chloride micropore to described barrier film
One of film, polyethene microporous membrane, glass fibre.
7. a kind of water system Na ion chargeable capacitor batteries based on titanium phosphorous oxides negative material according to claim 1, its
It is characterised by, the described water system Na ion chargeable capacitor batteries preparation method based on titanium phosphorous oxides negative material, including following
Step：
(1) with manganese dioxide as manganese source, sodium carbonate be sodium source, lithium carbonate, aluminium hydroxide, ferric nitrate, chromic nitrate, nickel nitrate or
Copper hydrate be the 3rd source, by three's mixed grinding, tabletting, at 500 DEG C calcining 5h, grind again, tabletting, at 850-900 DEG C
Lower calcining 12h, then deionized water and absolute ethanol washing successively, dry at 60 DEG C, obtain sodium manganese oxide；
(2) sodium manganese oxide prepared by step (1) is added in dehydrated alcohol, mix homogeneously, add conductive agent and binding agent,
Mix, tabletting, dry, obtain positive pole；
(3) with titanium sulfate as titanium source, disodium hydrogen phosphate as phosphorus source, after both are mixed, add sodium carbonate, heating in water bath is to solvent
Volatilization is complete, deionized water and absolute ethanol washing successively, dries, and calcining obtains titanium phosphorous oxides；
(4) titanium phosphorous oxides prepared by step (3) is added in dehydrated alcohol, mix homogeneously, add conductive agent and binding agent,
Mix, tabletting, dry, obtain negative pole；
(5) negative pole and electrolyte assembling prepared by the positive pole prepared step (2) successively, barrier film, step (4), form and are based on titanium
The water system Na ion chargeable capacitor batteries of phosphorous oxides negative material.
8. a kind of water system Na ion chargeable capacitor batteries based on titanium phosphorous oxides negative material according to claim 7, its
It is characterised by：The mol ratio of the manganese source, sodium source and the 3rd source of described step (1) is 0.22-0.44:0.9-1:0-0.1.
9. a kind of water system Na ion chargeable capacitor batteries based on titanium phosphorous oxides negative material according to claim 7, its
It is characterised by：The mol ratio of the titanium source of described step (3) and phosphorus source is 1:1-2.
10. a kind of water system Na ion chargeable capacitor batteries based on titanium phosphorous oxides negative material according to claim 7, its
It is characterised by：The mass ratio of the titanium phosphorous oxides in sodium manganese oxide and negative pole in the positive pole of described step (5) is 1.5-2.5:
1.
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| CN108336334A (en) * | 2018-02-05 | 2018-07-27 | 天津理工大学 | A kind of preparation method of high-performance sodium-ion battery positive material |
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| CN110783621A (en) * | 2019-10-18 | 2020-02-11 | 扬州扬达新能源有限公司 | Water system sodium ion battery and preparation method thereof |
| CN111244415A (en) * | 2020-01-16 | 2020-06-05 | 桂林电子科技大学 | Air-Stable Layered Transition Metal Oxide Cathode Materials and Their Na-ion Batteries |
| CN114361439A (en) * | 2021-11-29 | 2022-04-15 | 江苏理工学院 | Preparation method and application of a new type of electrode material for aqueous zinc ion battery |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108336334A (en) * | 2018-02-05 | 2018-07-27 | 天津理工大学 | A kind of preparation method of high-performance sodium-ion battery positive material |
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| CN110336026A (en) * | 2019-06-11 | 2019-10-15 | 中国电力科学研究院有限公司 | Preparation method of water-based sodium-ion battery cathode material and water-based sodium-ion battery |
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| CN111244415A (en) * | 2020-01-16 | 2020-06-05 | 桂林电子科技大学 | Air-Stable Layered Transition Metal Oxide Cathode Materials and Their Na-ion Batteries |
| CN114361439A (en) * | 2021-11-29 | 2022-04-15 | 江苏理工学院 | Preparation method and application of a new type of electrode material for aqueous zinc ion battery |
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