CN108461832A - A kind of water-system alkali metal ion battery and preparation method thereof based on colloid or gel electrolyte - Google Patents
A kind of water-system alkali metal ion battery and preparation method thereof based on colloid or gel electrolyte Download PDFInfo
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- CN108461832A CN108461832A CN201710097048.2A CN201710097048A CN108461832A CN 108461832 A CN108461832 A CN 108461832A CN 201710097048 A CN201710097048 A CN 201710097048A CN 108461832 A CN108461832 A CN 108461832A
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- colloid
- alkali metal
- electrolyte
- water
- metal ion
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- 239000000084 colloidal system Substances 0.000 title claims abstract description 71
- 239000011245 gel electrolyte Substances 0.000 title claims abstract description 49
- 229910001413 alkali metal ion Inorganic materials 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 239000003792 electrolyte Substances 0.000 claims abstract description 58
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 9
- 239000012530 fluid Substances 0.000 claims abstract description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 24
- 239000000463 material Substances 0.000 claims description 22
- 150000002500 ions Chemical class 0.000 claims description 18
- 239000011734 sodium Substances 0.000 claims description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 239000003292 glue Substances 0.000 claims description 11
- 239000000654 additive Substances 0.000 claims description 10
- 230000000996 additive effect Effects 0.000 claims description 10
- 239000003513 alkali Substances 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 9
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 9
- 229910052783 alkali metal Inorganic materials 0.000 claims description 9
- 150000001340 alkali metals Chemical class 0.000 claims description 9
- 230000003750 conditioning effect Effects 0.000 claims description 9
- 239000004020 conductor Substances 0.000 claims description 9
- 229910002804 graphite Inorganic materials 0.000 claims description 9
- 239000010439 graphite Substances 0.000 claims description 9
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 8
- 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 8
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Inorganic materials O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 8
- 229910052708 sodium Inorganic materials 0.000 claims description 8
- 239000006230 acetylene black Substances 0.000 claims description 7
- 239000002585 base Substances 0.000 claims description 7
- 150000003839 salts Chemical class 0.000 claims description 7
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Chemical compound [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 claims description 6
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 6
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 6
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 6
- 239000002202 Polyethylene glycol Substances 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 229920001223 polyethylene glycol Polymers 0.000 claims description 5
- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Substances [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 5
- 229910002012 Aerosil® Inorganic materials 0.000 claims description 4
- 229910019441 NaTi2(PO4)3 Inorganic materials 0.000 claims description 4
- 235000011187 glycerol Nutrition 0.000 claims description 4
- 229920002401 polyacrylamide Polymers 0.000 claims description 4
- 229960003351 prussian blue Drugs 0.000 claims description 4
- 239000013225 prussian blue Substances 0.000 claims description 4
- 229910014485 Na0.44MnO2 Inorganic materials 0.000 claims description 3
- 239000007832 Na2SO4 Substances 0.000 claims description 3
- 229910019338 NaMnO2 Inorganic materials 0.000 claims description 3
- -1 Prussian-blue compound Chemical class 0.000 claims description 3
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 claims description 3
- 229910000397 disodium phosphate Inorganic materials 0.000 claims description 3
- 150000007529 inorganic bases Chemical class 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
- 150000007522 mineralic acids Chemical class 0.000 claims description 3
- 150000007524 organic acids Chemical class 0.000 claims description 3
- 150000007530 organic bases Chemical class 0.000 claims description 3
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 claims description 3
- 229910052939 potassium sulfate Inorganic materials 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 3
- 239000011780 sodium chloride Substances 0.000 claims description 3
- 239000001509 sodium citrate Substances 0.000 claims description 3
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 3
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims description 3
- BAZAXWOYCMUHIX-UHFFFAOYSA-M sodium perchlorate Chemical compound [Na+].[O-]Cl(=O)(=O)=O BAZAXWOYCMUHIX-UHFFFAOYSA-M 0.000 claims description 3
- 229910001488 sodium perchlorate Inorganic materials 0.000 claims description 3
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 3
- 229910000406 trisodium phosphate Inorganic materials 0.000 claims description 3
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 2
- 238000005516 engineering process Methods 0.000 abstract description 5
- 229910052799 carbon Inorganic materials 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 5
- 238000005868 electrolysis reaction Methods 0.000 description 5
- 239000000835 fiber Substances 0.000 description 5
- 238000011049 filling Methods 0.000 description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 235000011152 sodium sulphate Nutrition 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000001413 cellular effect Effects 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 239000011147 inorganic material Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052755 nonmetal Inorganic materials 0.000 description 2
- 239000011368 organic material Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M potassium chloride Inorganic materials [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- VPGWWDZBZDPONV-UHFFFAOYSA-N 2-aminobutanedioic acid;sodium Chemical compound [Na].OC(=O)C(N)CC(O)=O VPGWWDZBZDPONV-UHFFFAOYSA-N 0.000 description 1
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 description 1
- 241000872198 Serjania polyphylla Species 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 150000002085 enols Chemical class 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 229920000831 ionic polymer Polymers 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- DCYOBGZUOMKFPA-UHFFFAOYSA-N iron(2+);iron(3+);octadecacyanide Chemical compound [Fe+2].[Fe+2].[Fe+2].[Fe+3].[Fe+3].[Fe+3].[Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] DCYOBGZUOMKFPA-UHFFFAOYSA-N 0.000 description 1
- 239000011244 liquid electrolyte Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- 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
-
- 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
- H01M10/38—Construction or manufacture
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
-
- 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
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Landscapes
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
Abstract
The present invention relates to a kind of water-system alkali metal ion battery and preparation method thereof based on colloid or gel electrolyte, the battery include：Colloid or gel electrolyte；Anode, cathode and the diaphragm between the positive electrode and negative electrode；And the plus plate current-collecting body and negative current collector being connected respectively with the anode and cathode；Without fluid media (medium).The present invention is that water system electrolyte is substituted for colloid or gel electrolyte, is easier to produce in original technology and technique, and cost is relatively low.
Description
Technical field
The present invention relates to a kind of water-system alkali metal ion battery and preparation method thereof based on colloid or gel electrolyte belongs to
In secondary cell field, technical field of energy material is also belonged to.
Background technology
With modern industry and economic rapid development, a large amount of uses of fossil energy, environment is made constantly to deteriorate, meanwhile,
Energy supply and demand problem is enabled to become increasingly conspicuous.Thus, seek more cleaning, efficient alternative energy source is that social urgent need to resolve is asked instantly
Topic.Wind-power electricity generation, solar power generation as a kind of clean energy resource, but due to be distributed it is more dispersed, be difficult to grid-connected, generating dutation with
The problems such as electricity consumption Time Inconsistency, electric energy can not be utilized efficiently because can not effectively store.
Water-system alkali metal ion battery is to solve the problems, such as this alternative, Whitacre (document 1, Whitacre,
J.F.,et al.,A Polyionic,Large-Format Energy Storage Device Using an Aqueous
Electrolyte and Thick-Format Composite NaTi2(PO4)3/Activated Carbon Negative
Electrodes.Energy Technology,2015.3(1):P.20-31), (document 2, Cao Yi, Xia Yongyao wait to Xia Yongyao
Present situation and prospect [J] energy storage science and technologies of water system sodium-ion battery, 2016,5) it is et al. the domestic and international area research ratio
Compared with front-runner, but the water-system alkali metal ion battery that they study at present must all use aqueous electrolyte, in aqueous solution,
Liberation of hydrogen, oxygen evolution reaction can occur when reaching certain potentials during alkali metal ion insertion deintercalation, and further break electrolysis
Matter acid-base balance accelerates the corrosion of battery afflux liquid, and so that battery capacity is decayed, fast, cycle life is low.
Invention content
In view of the above-mentioned problems, the purpose of the present invention is to provide a kind of water system alkali metal based on colloid or gel electrolyte
Ion battery and preparation method thereof.
On the one hand, the present invention provides a kind of water-system alkali metal ion battery based on colloid or gel electrolyte, it is described
Battery includes：Colloid or gel electrolyte；Anode, cathode and the diaphragm between the positive electrode and negative electrode；And respectively with
The plus plate current-collecting body and negative current collector that the anode is connected with cathode；Without fluid media (medium).
Present invention colloidal electrolyte or gel electrolyte replace the aqueous solution electrolysis of traditional water-system alkali metal ion battery
Matter, the colloidal electrolyte or gel electrolyte are that colloidal gel forms skeleton, and alkali metal ion is present in skeletal internal, and
It shuttles between skeleton in battery operation.On the one hand, colloidal electrolyte or gel electrolyte can improve electrolyte ion concentration, together
When low temperature when inhibit electrolyte ion to be precipitated, keep higher electrolyte concentration at low temperature, so improve battery specific energy (compared with
High electrolyte concentration can inhibit side reaction, improve battery specific energy, but in aqueous solution, electrolyte height to a certain extent it
Slightly cool down afterwards and just will appear crystallization, electrolyte concentration is caused to decline.The presence of gel skeleton in colloidal electrolyte, can increase
The steric hindrance of crystallization improves electrolyte ion concentration to inhibit crystallization).On the other hand, colloidal electrolyte or gel electrolyte
Matter is colloid or gel, and no fluid media (medium) makes positive and negative anodes be respectively formed oneself independent acid-base value so that positive and negative anodes PH is obtained
Independent control can play the role of inhibiting liberation of hydrogen, analysis oxygen when acid-base value changes to a certain extent, and then weaken collector
Burn into inhibits battery capacity decaying, improves battery cycle life.In addition, the battery of the present invention also has No leakage, shape can
Control, battery raw material abundance, it is environmental-friendly, cheap the advantages that.In addition, the present invention is that water system electrolyte is replaced plastic
Body or gel electrolyte are easier to produce in original technology and technique, and cost is relatively low.Meanwhile such as often occurring
Jolt in inclined environment, electrolyte type battery can not normal use, the battery of this structure can be used normally.
Preferably, the material that just extremely alkali metal ion can be embedded in and deviate from, preferably sodium base prussian blue
Close object, λ-MnO2、Na0.22MnO2、Na0.44MnO2、NaMnO2At least one of.
Preferably, the cathode is the material that alkali metal ion can be embedded in and deviate from, preferably (TiO)2P2O7、NaTi2
(PO4)3At least one of.
Preferably, also contain electronic conductive material in the anode and/or cathode, the electronic conductive material be graphite,
At least one of carbon black, acetylene black and metal powder.
Preferably, the colloid or gel in the colloid or gel electrolyte are water system organic colloid and/or gel, water system
At least one of inorganic colloid and/or gel, the water system organic colloid and/or gel are polyacrylamide gel, poly- second
At least one of enol cellulose colloid, the aqueous inorganic colloid and/or gel are that aerosil disperses to be formed
At least one of colloid, Ludox and silica sol.
Preferably, the alkali metal ion source in the colloid or gel electrolyte is the alkali and/or salt of alkali metal containing ion,
Preferably Na2SO4、NaCl、NaNO3、Na3PO4、Na2HPO4、NaH2PO4、NaC2H3O2、Na2C2O4、NaClO4、NaOH、K2SO4、
KCl、KNO3、KOH、Li2CO3、Li2SO4, at least one of LiOH.The collector material can be metal and nonmetal conduction material
Material, preferably at least one of copper, aluminium, nickel, graphite paper, stainless steel, plus plate current-collecting body and negative current collector material can phases
Together, it can also be different.The diaphragm can be high-molecular organic material, inorganic material, preferably fibre diaphragm, nonwoven cloth diaphragm,
At least one of cellular plastic diaphragm.
Preferably, the colloid or gel electrolyte also contain additive, the additive is glycerine, sodium citrate, Asia
At least one of aminosuccinic acid sodium, polyethylene glycol.
Preferably, the colloid or gel electrolyte also contain PH conditioning agents, the PH conditioning agents are organic acid, inorganic
Acid, organic base, inorganic base and at least one of the substance that acid or alkali can be generated indirectly.
On the other hand, the present invention also provides a kind of water-system alkali metal ion batteries based on colloid or gel electrolyte
Preparation method, which is characterized in that including：Anode, cathode, diaphragm and collector are assembled into battery, are placed in shell, glue is injected
Body electrolyte forms the water-system alkali metal ion battery based on colloid or gel electrolyte through gel process.
Preferably, mass percent shared by the colloidal electrolyte each component is：Solute 0.1%~55% contained by colloid,
Preferably 1%~45%；The alkali and/or salt 0.1%~50% of alkali metal containing ion, preferably 1%~40%；Additive
0.05%~15%, preferably 0.1%~11%；PH conditioning agents 0.05~10%, preferably 0.1%~7%.
Preferably, the shell includes：For the battery case of the filling colloid or gel electrolyte and for encapsulating
State the battery cover of battery case.
Description of the drawings
Fig. 1 is the water-system alkali metal ion battery based on colloid or gel electrolyte according to an implementation form of the invention
Structural schematic diagram；
Fig. 2 is λ-MnO in embodiment 12Anode, (TiO)2P2O7For cathode, current density 1mA/cm2Under charging and discharging curve
Figure；
Symbol description：
1 it is plus plate current-collecting body, 2 be anode pole piece (anode), 3 be diaphragm, 4 be cathode pole piece (cathode), 5 is negative current collector, 6
It is battery case for colloidal electrolyte or gel electrolyte, 7,8 is battery cover.
Specific implementation mode
It is further illustrated the present invention below by way of following embodiments, it should be appreciated that following embodiments are merely to illustrate this
Invention, is not intended to limit the present invention.
Water-system alkali metal ion battery provided by the invention based on colloid or gel electrolyte includes mainly：Colloid is solidifying
Glue electrolyte；It is placed in the anode in the electrolyte, cathode and the diaphragm between the positive electrode and negative electrode；And respectively
The plus plate current-collecting body and negative current collector being connected with the anode and cathode；Without fluid media (medium).Specifically, as shown in Figure 1, originally
The water-system alkali metal ion battery (hereinafter referred to as " battery ") based on colloid or gel electrolyte of invention, including：Shell, glue
Body electrolyte or gel electrolyte 6 and the pole group being set in the colloidal electrolyte or gel electrolyte 6, the pole group packet
It includes：Plus plate current-collecting body 1, anode 2, cathode 4, the diaphragm 3 between the anode and cathode and negative current collector 5.The glue
Contain alkali metal ion in body electrolyte or gel electrolyte.The form of the shell is unlimited, it may include is used for the filling glue
The battery case 7 of body electrolyte or gel electrolyte and the battery cover 8 for encapsulating the battery case, also can be selected integral type shell
Body etc..
In the present invention, the electrolyte (colloidal electrolyte or gel electrolyte) is the colloid or gel of alkali metal containing ion
Electrolyte, no liquid or fluid media (medium), anode, cathode and diaphragm are placed in the colloid or gel electrolyte.That is, electrolyte
Not exist in the form of a solution, and exists in the form of colloid or gel.The colloidal electrolyte or gel electrolyte are colloid
Gel-forming skeleton, alkali metal ion is present in skeletal internal, and shuttles between skeleton in battery operation.Alkali metal ion is made
For embedding de- positive and negative pole material receiving and losing electrons carrier, electrolyte leakage phenomenon, safe, controlled shape not will produce.The present invention
Described in battery the aqueous electrolyte of traditional water-system alkali metal ion battery is replaced using colloidal electrolyte or gel electrolyte.
First, which can inhibit the electrolysis of water system ion battery water in charging；Secondly, colloid can make positive and negative anodes PH obtain
Independent control, while the corrosion of collector can be inhibited；Again, colloid can improve electrolyte ion concentration, meanwhile, when low temperature
Electrolyte ion is inhibited to be precipitated.
Alkali metal ion in the colloidal electrolyte or gel electrolyte is in the alkali and/or salt of alkali metal containing ion
At least one, preferably Na2SO4、NaCl、NaNO3、Na3PO4、Na2HPO4、NaH2PO4、NaC2H3O2、Na2C2O4、NaClO4、
NaOH、K2SO4、KCl、KNO3、KOH、Li2CO3、Li2SO4, at least one of LiOH etc..The alkali of the alkali metal containing ion
And/or salt can account for the 0.1%~50% of colloidal electrolyte or gel electrolyte gross mass, preferably 1%~40%.The colloid
The colloid of electrolyte or gel electrolyte is selected from least one of water system organic colloid and/or aqueous inorganic colloid.And according to
At least one additive of demand addition, for improving battery performance.Meanwhile at least one PH conditioning agents are added according to demand, it uses
PH value near adjusting positive and negative anodes.The water system organic colloid can be vinal element colloid, polyacrylamide gel
Can be that aerosil disperse the colloid to be formed, Ludox, silica sol etc. Deng, aqueous inorganic colloid.Contained by the colloid
Solute can account for the 0.1%~55% of colloidal electrolyte or gel electrolyte gross mass, preferably 1%~45%.The PH is adjusted
Agent can be at least one of organic acid, inorganic acid, organic base, inorganic base etc., preferably, hydrochloric acid, acetic acid, sodium hydroxide etc..
The PH conditioning agents can account for the 0.05~10% of colloidal electrolyte or gel electrolyte gross mass, preferably 0.1%~7%.Institute
It states additive and can be selected from least one of glycerine, sodium citrate, cinic acid sodium, polyethylene glycol etc..The additive
Content can account for the 0.05%~15% of colloidal electrolyte or gel electrolyte gross mass, preferably 0.1%~11%.
In the present invention, the material that just extremely alkali metal ion can be embedded in and deviate from.The anode alkali metal ion can
Embedded and abjection material is the material with relatively high embedding/de- potential plateau that alkali metal ion can be embedded in and deviate from, can
Using sodium base Prussian-blue compound, λ-MnO2、Na0.22MnO2、Na0.44MnO2、NaMnO2One or more of equal materials.
The sodium base Prussian-blue compound, general formula NaxMyFe(CN)6, wherein M can be Fe, Co, Ni, Cu, Zn, Ti, V, Cr,
One or more of Mn, 0≤x≤4,0≤y≤2.
In the present invention, the cathode is the material that alkali metal ion can be embedded in and deviate from, and as alkali metal ion can be embedded in
With the material with relatively low embedding/de- potential plateau of abjection, can be used (TiO)2P2O7、NaTi2(PO4)3In equal materials
It is one or more of.
In addition, suitable electronic conductive material can be also added in positive or negative pole, such as graphite, carbon black, acetylene black, metal
Powder or other conductive materials.Mass percent shared by electronic conductive material is 0.1%~20% in positive or negative pole, preferably
2%~10%.In addition, positive or negative pole itself can also be coated by electronic conductive material.
In the present invention, the collector material can be metal and nonmetal conductive material, preferably copper, aluminium, nickel, graphite paper,
At least one of stainless steel, plus plate current-collecting body and negative current collector material may be the same or different.The anode collection
The thickness of body or negative current collector is adjustable as needed, may generally be 5 μm~2000 μm.
In the present invention, the diaphragm can be high-molecular organic material, inorganic material, preferably fibre diaphragm, non-woven fabrics every
One or more of film, cellular plastic diaphragm etc..The thickness of the diaphragm can as needed it is adjustable, may generally be 5 μm~
5000μm。
Illustrate to following exemplary the system of the water-system alkali metal ion battery of colloid or gel electrolyte provided by the invention
Preparation Method.
Anode, cathode, diaphragm and collector are assembled into battery, are placed in the effigurate container (shell) of tool, note
Enter colloidal electrolyte, through gel process, forms the water-system alkali metal ion battery based on colloid or gel electrolyte.The colloid
Mass percent shared by electrolyte each component can be：Solute 0.1%~55% contained by colloid, preferably 1%~45%；Containing alkali gold
The alkali and/or salt 0.1%~50% of category ion, preferably 1%~40%；Additive 0.05%~15%, preferably 0.1%~
11%；PH conditioning agents 0.05~10%, preferably 0.1%~7%.
In addition, extraction wire can be distinguished from negative current collector and plus plate current-collecting body, for being connected with load, thus to load
Power supply.
The present invention directly uses colloidal electrolyte or gel electrolyte to replace the water-soluble of traditional water-system alkali metal ion battery
Liquid electrolyte, the battery can inhibit the electrolysis of water system ion battery water in charging；Secondly, colloid can make positive and negative anodes PH
It is independently controlled, while the corrosion of collector can be inhibited；Again, colloid can improve electrolyte ion concentration, meanwhile, it is low
Electrolyte ion is inhibited to be precipitated when warm.Again simultaneously, battery has No leakage, controlled shape, battery raw material abundance, environment friend
The advantages that good, cheap.
Embodiment is enumerated further below so that the present invention will be described in detail.It will similarly be understood that following embodiment is served only for this
Invention is further described, and should not be understood as limiting the scope of the invention, those skilled in the art is according to this hair
Some nonessential modifications and adaptations that bright the above is made all belong to the scope of protection of the present invention.Following examples are specific
Technological parameter etc. is also only an example in OK range, i.e. those skilled in the art can be done properly by the explanation of this paper
In the range of select, and do not really want to be defined in hereafter exemplary concrete numerical value.
Embodiment 1：
Such as Fig. 1, a kind of water-system alkali metal ion battery based on colloid or gel electrolyte, anode use mass percent for
94% carbon coating λ-MnO2Anode pole piece is made in graphite with 6%；Cathode use mass percent for 8% graphite, 1%
Acetylene black, 91% carbon coating (TiO)2P2O7Cathode pole piece is made；Using 9% sodium sulphate, 19% aerosil,
0.3% polyethylene glycol, 0.4% remaining ratio of cinic acid sodium are water, and colloidal electrolyte is made.It presses successively from left to right
The sequence assembling of plus plate current-collecting body, positive electrode, fibre diaphragm, negative material, negative current collector, and filling above-mentioned colloid electrolysis
Matter, through gel process, at full battery.As shown in Fig. 2, being 1mA/cm in current density2It tests and finds under conditions of lower, once fill
After electric discharge, anode PH=6.47, cathode PH=8.13；Electrode is nearby without any gas evolution phenomenon.
Embodiment 2
Such as Fig. 1, a kind of water-system alkali metal ion battery based on colloid or gel electrolyte, anode use mass percent for
96% carbon coating Na2NiFe(CN)6Anode pole piece is made in acetylene black with 4%；Cathode use mass percent for 3% stone
Ink, 7% acetylene black, 90% carbon coating NaTi2(PO4)3Cathode pole piece is made；Using 9% sodium sulphate, 19% gas phase
Silica, 0.3% polyethylene glycol, 0.4% remaining ratio of cinic acid sodium are water, and colloidal electrolyte is made.From a left side
Turn right successively by plus plate current-collecting body, positive electrode, fibre diaphragm, negative material, negative current collector sequence assemble, and it is filling on
Colloidal electrolyte is stated, through gel process, at full battery.
Embodiment 3
Such as Fig. 1, a kind of water-system alkali metal ion battery based on colloid or gel electrolyte, anode use mass percent for
94% carbon coating λ-MnO2Anode pole piece is made in graphite with 6%；Cathode use mass percent for 8% graphite, 1%
Acetylene black, 91% carbon coating (TiO)2P2O7Cathode pole piece is made；Using 7% sodium sulphate, 0.6% glycerine, 0.1% hydrogen
Sodium oxide molybdena, remaining is that solid content is 17% polyacrylamide colloid, and colloidal electrolyte is made.Press anode collection successively from left to right
The sequence assembling of body, positive electrode, fibre diaphragm, negative material, negative current collector, and filling above-mentioned colloidal electrolyte, through solidifying
Glue process, at full battery.
Example the above is only the implementation of the present invention is not intended to limit the scope of the invention, every to utilize this hair
The equivalent structure or equivalent flow shift that bright specification and accompanying drawing content are done is applied directly or indirectly in other relevant skills
Art field, is included within the scope of the present invention.
Claims (10)
1. a kind of water-system alkali metal ion battery based on colloid or gel electrolyte, which is characterized in that the battery includes：
Colloid or gel electrolyte；
Anode, cathode and the diaphragm between the positive electrode and negative electrode；And
The plus plate current-collecting body and negative current collector being connected respectively with the anode and cathode；
Without fluid media (medium).
2. water-system alkali metal ion battery according to claim 1, which is characterized in that described just extremely alkali metal ion can
Embedded and abjection material, preferably sodium base Prussian-blue compound, λ-MnO2、Na0.22MnO2、Na0.44MnO2、NaMnO2In
At least one.
3. water-system alkali metal ion battery according to claim 1 or 2, which is characterized in that the cathode be alkali metal from
The material that son can be embedded in and deviate from, preferably (TiO)2P2O7、NaTi2(PO4)3At least one of.
4. water-system alkali metal ion battery according to any one of claim 1-3, which is characterized in that it is described anode and/
Or also contain electronic conductive material in cathode, the electronic conductive material be graphite, carbon black, acetylene black and metal powder in extremely
Few one kind.
5. the water-system alkali metal ion battery according to any one of claim 1-4, which is characterized in that the colloid is solidifying
Colloid or gel in glue electrolyte are at least one in water system organic colloid and/or gel, aqueous inorganic colloid and/or gel
Kind, the water system organic colloid and/or gel are at least one of polyacrylamide gel, vinal element colloid,
The aqueous inorganic colloid and/or gel are that aerosil disperses in the colloid to be formed, Ludox and silica sol extremely
Few one kind.
6. water-system alkali metal ion battery according to any one of claims 1-5, which is characterized in that the colloid is solidifying
Alkali metal ion source in glue electrolyte is the alkali and/or salt of alkali metal containing ion, preferably Na2SO4、NaCl、NaNO3、
Na3PO4、Na2HPO4、NaH2PO4、NaC2H3O2、Na2C2O4、NaClO4、NaOH、K2SO4、KCl、KNO3、KOH、Li2CO3、
Li2SO4, at least one of LiOH.
7. the water-system alkali metal ion battery according to any one of claim 1-6, which is characterized in that the colloid is solidifying
Glue electrolyte also contains additive, the additive be in glycerine, sodium citrate, cinic acid sodium, polyethylene glycol extremely
Few one kind.
8. the water-system alkali metal ion battery according to any one of claim 1-7, which is characterized in that the colloid is solidifying
Glue electrolyte also contains PH conditioning agents, and the PH conditioning agents are organic acid, inorganic acid, organic base, inorganic base and can be indirect
Generate at least one of the substance of acid or alkali.
9. the water-system alkali metal ion battery based on colloid or gel electrolyte described in a kind of any one of claim 1-8
Preparation method, which is characterized in that including：Anode, cathode, diaphragm and collector are assembled into battery, are placed in shell, glue is injected
Body electrolyte forms the water-system alkali metal ion battery based on colloid or gel electrolyte through gel process.
10. preparation method according to claim 9, which is characterized in that quality hundred shared by the colloidal electrolyte each component
Point ratio is：Solute 0.1%~55% contained by colloid, preferably 1%~45%；The alkali and/or salt 0.1%~50% of alkali metal containing ion,
Preferably 1%~40%；Additive 0.05%~15%, preferably 0.1%~11%；PH conditioning agents 0.05~10%, preferably 0.1%~
7%。
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| CN111883857A (en) * | 2020-07-22 | 2020-11-03 | 厦门理工学院 | Colloidal electrolyte and zinc ion battery comprising same |
| CN114520375A (en) * | 2022-02-16 | 2022-05-20 | 常州优特科新能源科技有限公司 | Gel electrolyte with liquid retention function for air separator |
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