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 PDF

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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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sodium
titanium
phosphorous oxides
ion
water system
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李风浪
李舒歆
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Dongguan Lianzhou Intellectual Property Operation and Management Co Ltd
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Dongguan Lianzhou Intellectual Property Operation and Management Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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 OR LIGHT-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 OR LIGHT-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 OR LIGHT-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 OR LIGHT-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

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

A kind of water system Na ion chargeable capacitor batteries based on titanium phosphorous oxides negative material
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.
CN201610938549.4A 2016-10-25 2016-10-25 Aqueous rechargeable sodium-ion capacitor battery based on titanium phosphorus oxide cathode material Pending CN106384674A (en)

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Cited By (5)

* Cited by examiner, † Cited by third party
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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 The preparation method and water system sodium-ion battery of water system sodium-ion battery positive material
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 positive electrode material and sodium ion battery thereof
CN114361439A (en) * 2021-11-29 2022-04-15 江苏理工学院 Preparation method and application of novel water-based zinc ion battery electrode material

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
CN108336334B (en) * 2018-02-05 2020-09-22 天津理工大学 Preparation method of sodium ion battery positive electrode material
CN110336026A (en) * 2019-06-11 2019-10-15 中国电力科学研究院有限公司 The preparation method and water system sodium-ion battery of water system sodium-ion battery positive material
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 positive electrode material and sodium ion battery thereof
CN114361439A (en) * 2021-11-29 2022-04-15 江苏理工学院 Preparation method and application of novel water-based zinc ion battery electrode material

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