CN107871861A - A kind of water system sodium ion electrochemical energy storage device - Google Patents
A kind of water system sodium ion electrochemical energy storage device Download PDFInfo
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- CN107871861A CN107871861A CN201710340322.4A CN201710340322A CN107871861A CN 107871861 A CN107871861 A CN 107871861A CN 201710340322 A CN201710340322 A CN 201710340322A CN 107871861 A CN107871861 A CN 107871861A
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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
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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Abstract
The present invention relates to a kind of water system sodium ion electrochemical energy storage device, belong to electrochemical energy storage field.The device includes positive pole, negative pole, barrier film and aqueous phase electrolyte, and the active material of the positive pole is with formula AB2O4Compound, and there is spinel structure, wherein A is selected from more than one or both of Li, Na, Zn, Cu, Ni and Ti；B is selected from more than one or both of Mn, Co, Al and Fe.Meanwhile the positive electrode active materials have effective specific capacity Reversible Cycle more than 80mAh/g.The water system sodium ion electrochemical energy storage device of the present invention has the characteristics that the cycle life of length, environmentally safe, security performance is high, raw material sources are extensive, price is low.
Description
Technical field
The present invention relates to a kind of water system sodium ion electrochemical energy storage device, belong to electrochemical energy storage field.
Background technology
Social economy is also improving constantly in high speed development, the mankind to the interdependency of the energy.According to statistics, the present world
The 70% of annual energy resource consumption total amount derives from fossil energy (oil, coal, natural gas).But the burning of fossil fuel can produce greatly
The harmful substance of amount, not only pollutes the environment, and also serious threat the survival and development of human society.So human society face
The primary problem faced is to change irrational energy resource structure, while the energy for wanting Devoting Major Efforts To Developing to clean, and progressively to replace fossil energy
Source.Developing solar energy, wind energy, geothermal energy, this kind of reproducible clean energy resource of tide energy turns into the heat of current every country concern
Point.Regenerative resource is had a great influence by weather and period, have the characteristics that it is obvious unstable, discontinuous and uncontrollable,
Need to develop and build supporting energy storage device to ensure the stability for generating electricity, powering.Therefore, extensive energy storage skill
Art is to greatly develop the key of the renewable energy utilizations such as solar energy, wind energy and intelligent grid.
The energy storage technology of current main-stream mainly includes the energy storage of physics class and electrochemical energy storage, and wherein electrochemical energy storage has effect
Rate height, small investment, it is safe to use, using it is flexible the advantages that, very extensive research and application have been obtained, before there is good development
Scape.At present, lithium ion battery is the good high-energy battery system of development prospect, with energy density is big, discharge voltage is high, puts certainly
Electric rate is low, environment-friendly, the advantages that having extended cycle life.But with the large-scale application of lithium ion battery, the demand meeting of lithium
It is increasing, due to reserves limited in the earth's crust, cause the price of lithium material can more and more higher.Because sodium and lithium are in same master
Race, there are similar electrochemical properties, and rich reserves of the sodium in the earth's crust, account for 2.74%, be the 6th abundant element, sodium
Base battery is expected to the alternative as lithium ion battery.It is the same with lithium ion battery as the energy storage system of a new generation, safety
Sex chromosome mosaicism is the emphasis that we pay close attention to.Select different sodium salts and organic solvent and electrolyte is optimized, all can be to battery
Useful life, security performance and cycle performance produce certain influence.For lithium ion battery, the electricity of organic solvent class
Solution liquid achieves actual application in the battery of commercialization, but safety issue is always to restrict lithium ion battery development
Problem.This is primarily due to the flash-point of organic solvent than relatively low, inflammable, causes battery to be put etc. under extreme case overcharging, cross
The safety problem such as generation blast or burning.
Therefore, researching and developing safe, economic, high performance water system sodium ion energy storage device has very important meaning
Justice.
The content of the invention
For the deficiency of existing energy storage device technology, it is an object of the invention to provide one kind can be applied to energy storage market neck
Domain, green safe water system sodium ion electrochemical energy storage device.
The technical scheme is that：
A kind of water system sodium ion electrochemical energy storage device, including positive pole, negative pole, barrier film and water system phase electrolyte, positive pole
Active material is with formula AB2O4Compound, and there is spinel structure；Wherein, A is in Li, Zn, Cu, Ni and Ti
It is one or more kinds of；B is selected from more than one or both of Mn, Co, Al and Fe；Meanwhile the positive electrode active materials have
Effective specific capacity Reversible Cycle more than 80mAh/g.
Described water system sodium ion electrochemical energy storage device, the active material of positive pole assemble in water system electrochemical energy storing device
After preceding or assembling, the sodium ion exchange that all or part of chemistry or electrochemistry are carried out to component A is handled.
Described water system sodium ion electrochemical energy storage device, the active material of positive pole are selected from LiMn2O4、NiAl2O4、
ZnAl2O4、TiFe2O4、CuMn2O4One or both of more than mixture；Or metal or the nonmetallic member of the material
Plain dopant material.
Described water system sodium ion electrochemical energy storage device, the active material of negative pole includes can be in the aqueous electrolyte
In with sodium ion be embedded in-deviate from the material of electrochemical reaction, or be capable of adsorption-desorption sodium ion with high-specific surface area
Capacitative materials.
Described water system sodium ion electrochemical energy storage device, the active material of negative pole are selected from activated carbon, graphene, carbon sodium rice
Pipe, carbon fiber, mesoporous carbon, NaTi2(PO4)3、LiTi2(PO4)3One or both of more than mixture.
Described water system sodium ion electrochemical energy storage device, electrolyte are sodium-salt aqueous solution, and Na ion concentration be 0.1~
5mol/L。
Described water system sodium ion electrochemical energy storage device, sodium salt are selected from sodium sulphate, sodium nitrate, sodium halide, sodium carbonate, phosphorus
It is more than one or both of sour sodium, sodium acetate, sodium hydroxide, homo amino acid sodium.
Described water system sodium ion electrochemical energy storage device, electrolyte is additionally added supporting electrolyte, to improve electrolyte
Ionic conductivity and Ion transfer speed；The anion of supporting electrolyte is in sulfate radical, nitrate anion, chlorion or hydroxyl
One or more kinds of ions mixture；The cation of supporting electrolyte is in alkali metal ion, alkaline-earth metal ions
The mixture of one or more kinds of ions.
Described water system sodium ion electrochemical energy storage device, electrolyte is additionally added buffer electrolyte, for stablizing electrolyte
PH value after long-term work, buffer electrolyte are the strong base-weak acid salt of alkali metal ion.
Described water system sodium ion electrochemical energy storage device, in negative material, it is 1~10% to lead to be additionally added weight content
Electric agent and the binding agent that weight content is 1~10%, conductive agent is graphite, carbon black or acetylene black, and binding agent is polytetrafluoroethylene (PTFE)
Or Kynoar；In positive electrode, it is 1~10% to be additionally added conductive agent that weight content is 1~10% and weight content
Binding agent, conductive agent are graphite, carbon black or acetylene black, and binding agent is polytetrafluoroethylene (PTFE) or Kynoar.
Advantages of the present invention and beneficial effect are：
The water system sodium ion electrochemical energy storage device of the present invention has long cycle life, environmentally safe, security
Can be high, raw material sources are extensive, price is low the features such as, positive electrode active materials have follow reversible more than 80mAh/g effective specific capacity
Ring.
Embodiment
In specific implementation process, water system sodium ion electrochemical energy storage device of the present invention, including positive pole, negative pole, barrier film and
Water system phase electrolyte.Positive electrode active materials are with formula AB2O4Compound, and there is spinel structure, wherein A be selected from Li,
It is more than one or both of Zn, Cu, Ni and Ti；B is selected from more than one or both of Mn, Co, Al and Fe.It is meanwhile described
Positive electrode active materials have effective specific capacity Reversible Cycle more than 80mAh/g.Positive electrode active materials are in the water system electrochemistry
Before energy storage device assembling or after assembling, the sodium ion exchange that all or part of chemistry or electrochemistry are carried out to component A is handled.Its
In：
The active material of positive pole is selected from LiMn2O4、NiAl2O4、ZnAl2O4、TiFe2O4、CuMn2O4One or both of
Mixture above；Or the metal or nonmetal doping material of the material.The positive electrode also needs to add preferably
Material conductivity is improved for 5~10wt% conductive agent (graphite, carbon black or acetylene black etc.), while it is preferably 5 also to need to add
~10wt% binding agent (polytetrafluoroethylene (PTFE) or Kynoar etc.) come be made uniformly, the sticking mixing material of tool, then will
The mixing material is fixed on a current collector by pressure or conducting resinl, and collector includes stainless steel, nickel, titanium, aluminium, graphite fibre
Cloth etc..
The active material of negative pole includes can carrying out with sodium ion in the aqueous electrolyte being embedded in-and to deviate from electrochemistry anti-
The material answered, or the capacitative materials that there is high-specific surface area to be capable of adsorption-desorption sodium ion, selected from activated carbon, graphene, carbon
Sodium rice pipe, carbon fiber, mesoporous carbon, NaTi2(PO4)3、LiTi2(PO4)3One or both of more than mixture.The negative pole
Material also needs addition preferably 5~10wt% conductive agent (graphite, carbon black or acetylene black etc.) to improve material conductivity, simultaneously
Addition preferably 5~10wt% binding agent (polytetrafluoroethylene (PTFE) or Kynoar etc.) is also needed to be made uniformly, with viscosity
Mixing material, then the mixing material is fixed on a current collector by pressure or conducting resinl, collector include stainless steel,
Nickel, titanium, aluminium, graphite fiber cloth etc..
Electrolyte is sodium-salt aqueous solution, and Na ion concentration is 0.1~5mol/L.Sodium salt is selected from sodium sulphate, sodium nitrate, halogen
Change more than one or both of sodium, sodium carbonate, sodium phosphate, sodium acetate, sodium hydroxide, homo amino acid sodium.The electrolyte also adds
Enter appropriate supporting electrolyte, the supporting electrolyte anion be sulfate radical, nitrate anion, chlorion or hydroxyl in one kind or
The mixture of two or more ions；Cation is one or both of alkali metal ion, alkaline-earth metal ions above ion
Mixture.The electrolyte is additionally added appropriate buffer electrolyte, is 7~8 for stablizing the pH value after electrolyte long-term work,
Buffer electrolyte is the strong base-weak acid salt of alkali metal ion.
Barrier film between positive and negative electrode can use the porous septum on the secondary electric ground of existing water system, such as：Lead-acid accumulator is used
Fibreglass diaphragm, the porous polyphenyl alkene barrier film to use for nickel-hydrogen battery etc..
The present invention is discussed in detail for specific embodiment below, there is provided embodiment is for the ease of understanding the present invention, is definitely not
The limitation present invention.
Embodiment 1
In the present embodiment, positive electrode active materials use commercialized LiMn2O4.Positive pole is formed according to LiMn2O4：Acetylene black：
PVDF binding agent=80：10：10 part by weight mixed slurry, is evenly applied on nickel screen collector, is pressed into after drying
Electrode slice thick 0.4mm.Negative active core-shell material uses commercialized activated carbon, according to activated carbon：Acetylene black：PVDF binding agents=
80：10：10 part by weight mixed slurry, is evenly applied on nickel screen collector, and the thick electrodes of 0.4mm are pressed into after drying
Piece.Using analytically pure raw material, 0.5mol/L sodium sulphate electrolyte is configured, and include 0.1mol/L sodium acetates.By both positive and negative polarity electricity
Pole is cut according to specification, and using the barrier film of commercial Ni-MH battery and the electrolyte of above-mentioned configuration, pairing is assembled into battery.0~
1.6V operating voltages section carries out charge and discharge cycles test with 40mA/g current strength.First discharge specific capacity is 85.9mAh/g,
Efficiency is 85.7% first, after 200 circulations, capability retention 92.6%.
Embodiment 2
In the present embodiment, positive electrode active materials use NiAl2O4.Positive pole is formed according to NiAl2O4：Acetylene black：PVDF is bonded
Agent=80：10：10 part by weight mixed slurry, is evenly applied on nickel screen collector, and the thick electricity of 0.4mm is pressed into after drying
Pole piece.Negative active core-shell material uses commercialized activated carbon, according to activated carbon：Acetylene black：PVDF binding agent=80：10：10
Part by weight mixed slurry, is evenly applied on nickel screen collector, and the thick electrode slices of 0.4mm are pressed into after drying.Using analysis
Pure raw material, 1.0mol/L sodium sulphate electrolyte is configured, and include 0.1mol/L sodium acetates.Both positive and negative polarity electrode is cut out according to specification
Cut, using the barrier film of commercial Ni-MH battery and the electrolyte of above-mentioned configuration, pairing is assembled into battery.In 0~1.6V operating voltages
Section carries out charge and discharge cycles test with 40mA/g current strength.First discharge specific capacity is 81.0mAh/g, and efficiency is first
77.7%, after 200 circulations, capability retention 84.6%.
Embodiment 3
In the present embodiment, positive electrode active materials use commercialized LiMn2O4.Positive pole is formed according to LiMn2O4：Acetylene black：
PVDF binding agent=80：10：10 part by weight mixed slurry, is evenly applied on nickel screen collector, is pressed into after drying
Electrode slice thick 0.4mm.Negative active core-shell material uses NaTi2(PO4)3, according to NaTi2(PO4)3：Acetylene black：PVDF binding agents=
80：10：10 part by weight mixed slurry, is evenly applied on nickel screen collector, and the thick electrodes of 0.4mm are pressed into after drying
Piece.Using analytically pure raw material, 0.5mol/L sodium sulphate electrolyte is configured, and include 0.1mol/L sodium oxalates.By both positive and negative polarity electricity
Pole is cut according to specification, and using the barrier film of commercial Ni-MH battery and the electrolyte of above-mentioned configuration, pairing is assembled into battery.0~
1.6V operating voltages section carries out charge and discharge cycles test with 40mA/g current strength.First discharge specific capacity is 88.9mAh/g,
Efficiency is 95.4% first, after 200 circulations, capability retention 80.7%.
Embodiment result shows that apparatus of the present invention have long cycle life, and have environmentally safe, security
Can be high, raw material sources are extensive, price is low the features such as.
Above-mentioned embodiment is to illustrate the features of the present invention, but the present invention is not limited to above-described embodiment,
In those of ordinary skill in the art's possessed knowledge, it can also be made on the premise of present inventive concept is not departed from
Various change, it also should be regarded as protection scope of the present invention.
Claims (10)
1. a kind of water system sodium ion electrochemical energy storage device, including positive pole, negative pole, barrier film and water system phase electrolyte, its feature exist
In the active material of positive pole is with formula AB2O4Compound, and there is spinel structure；Wherein, A be selected from Li, Zn, Cu,
It is more than one or both of Ni and Ti；B is selected from more than one or both of Mn, Co, Al and Fe；Meanwhile the positive pole is lived
Property material have more than 80mAh/g effective specific capacity Reversible Cycle.
2. water system sodium ion electrochemical energy storage device according to claim 1, it is characterised in that the active material of positive pole exists
Before the assembling of water system electrochemical energy storing device or after assembling, all or part of chemistry or the sodium ion of electrochemistry are carried out to component A
Exchange is handled.
3. water system sodium ion electrochemical energy storage device according to claim 1 or 2, it is characterised in that the active material of positive pole
Material is selected from LiMn2O4、NiAl2O4、ZnAl2O4、TiFe2O4、CuMn2O4One or both of more than mixture；Or institute
State the metal or nonmetal doping material of material.
4. water system sodium ion electrochemical energy storage device according to claim 1, it is characterised in that the active material bag of negative pole
Include with sodium ion be embedded in-deviate from the material of electrochemical reaction in the aqueous electrolyte, or has high-ratio surface
Product is capable of the capacitative materials of adsorption-desorption sodium ion.
5. the water system sodium ion electrochemical energy storage device according to claim 1 or 4, it is characterised in that the active material of negative pole
Material is selected from activated carbon, graphene, carbon nanometer tube, carbon fiber, mesoporous carbon, NaTi2(PO4)3、LiTi2(PO4)3In one kind or two
The mixture of the kind above.
6. water system sodium ion electrochemical energy storage device according to claim 1, it is characterised in that electrolyte is that sodium salt is water-soluble
Liquid, and Na ion concentration is 0.1~5mol/L.
7. water system sodium ion electrochemical energy storage device according to claim 6, it is characterised in that sodium salt be selected from sodium sulphate,
It is more than one or both of sodium nitrate, sodium halide, sodium carbonate, sodium phosphate, sodium acetate, sodium hydroxide, homo amino acid sodium.
8. water system sodium ion electrochemical energy storage device according to claim 1, it is characterised in that electrolyte is additionally added support
Electrolyte, to improve the ionic conductivity of electrolyte and Ion transfer speed；The anion of supporting electrolyte is sulfate radical, nitre
The mixture of one or both of acid group, chlorion or hydroxyl above ion；The cation of supporting electrolyte is alkali metal
The mixture of one or both of ion, alkaline-earth metal ions above ion.
9. water system sodium ion electrochemical energy storage device according to claim 1, it is characterised in that electrolyte is additionally added buffering
Electrolyte, for stablizing the pH value after electrolyte long-term work, buffer electrolyte is the strong base-weak acid salt of alkali metal ion.
10. water system sodium ion electrochemical energy storage device according to claim 1, it is characterised in that in negative material, also add
Enter the conductive agent that weight content is 1~10% and the binding agent that weight content is 1~10%, conductive agent is graphite, carbon black or second
Acetylene black, binding agent are polytetrafluoroethylene (PTFE) or Kynoar；In positive electrode, the conduction that weight content is 1~10% is additionally added
Agent and weight content are 1~10% binding agent, and conductive agent be graphite, carbon black or acetylene black, binding agent for polytetrafluoroethylene (PTFE) or
Kynoar.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109192978A (en) * | 2018-08-01 | 2019-01-11 | 池州精研新能源科技有限公司 | A kind of novel high-performance aqueous solution lithium/sodium-ion battery and preparation method thereof |
| CN109742476A (en) * | 2019-01-09 | 2019-05-10 | 东北师范大学 | A kind of recoverying and utilizing method of waste lithium ion cell anode material |
| CN112751009A (en) * | 2021-02-09 | 2021-05-04 | 福州大学 | Zinc aluminate porous carbon based negative electrode material for lithium ion battery and preparation method and application thereof |
| CN116093255A (en) * | 2023-02-20 | 2023-05-09 | 中国科学院长春应用化学研究所 | Battery system for evaluating lithium ion and sodium ion storage compatibility of positive electrode material |
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