CN102903917A - Aqueous electrolyte rechargeable zinc ion battery - Google Patents
Aqueous electrolyte rechargeable zinc ion battery Download PDFInfo
- Publication number
- CN102903917A CN102903917A CN2012103801426A CN201210380142A CN102903917A CN 102903917 A CN102903917 A CN 102903917A CN 2012103801426 A CN2012103801426 A CN 2012103801426A CN 201210380142 A CN201210380142 A CN 201210380142A CN 102903917 A CN102903917 A CN 102903917A
- Authority
- CN
- China
- Prior art keywords
- ion battery
- zinc
- zinc ion
- electrolyte
- battery
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- 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
Landscapes
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses an aqueous electrolyte rechargeable zinc ion battery, belonging to the technical field of battery preparation. The battery disclosed herein is characterized in that: the cathode active material mainly comprises zinc ions (Zn<2+>)- intercalated and -removed copper (nickel) ferricyanide, the anode active material mainly comprises zinc, and the electrolyte which is liquid or gel comprises soluble salts of zinc as the solute and water as the solvent. According to the invention, the zinc ions can be intercalated in the copper (nickel) ferricyanide cathode material lattices or be removed from the copper (nickel) ferricyanide cathode material lattices, simultaneously the anode material mainly comprising zinc is subject to oxidation or reduction, thus the battery has the characteristics of high specific capacity and rapid charging, and the battery can be widely applied in the fields of portable mobile terminal, equipment, miniature electric vehicle and automobile starting battery, etc.
Description
Technical field
The invention belongs to the battery preparing technical field, be specifically related to a kind of aqueous solution electrolysis liquid Rechargeable zinc ion battery.
Background technology
Along with the fast development of global economy, supply and the environmental problem of fossil fuel become increasingly conspicuous, so the comprehensive high-efficiency ground development and utilization of new green power become and ensure the national energy resource security, implement the key link of the national energy strategy of sustainable development.The primary cell of comparing, secondary cell can repeatedly carry out charge and discharge cycles, can take full advantage of raw material, so practical more economically.The rechargeable battery that is most widely used at present is lithium ion battery.Lithium ion battery utilizes lithium ion as the energy-accumulating medium store electrical energy, by the embedding of lithium ion between positive and negative pole material with deviate to realize discharging and recharging of battery.Along with the development of human society and the progress of science and technology, the kind of mobile electronic product and electric vehicle and quantity will constantly increase, demand to secondary cell also increases thereupon, so the development of new rechargeable battery is very necessary and significant.
Zinc is a kind of reactive metal, has cheapness, is easy to get, the characteristics such as process safety, has therefore received increasing concern with the zinc metal as the secondary cell of negative material.Chinese invention patent application CN101540417A discloses a kind of take manganese dioxide as anodal first, take zinc as negative pole, Rechargeable zinc ion battery take the solution that contains zinc ion as electrolyte, zinc ion is deviate from manganese dioxide when charging, then in the negative pole deposition, reversible reaction occurs during discharge through electrolyte.Owing to utilizing zinc and zinc ion as active material, electrode reaction is two electron reactions, and this battery has higher specific capacity.But because the lattice constant of manganese dioxide is less, relatively difficulty is deviate from the embedding of zinc ion, causes battery to embed with to deviate from process rate slower at the zinc ion of charge/discharge, makes the Zinc ion battery performance remain further to be improved.
Therefore, in order further to improve the Rechargeable zinc ion battery performance, seek and novel zinc ion is had good embedding/deviate from performance, cheap, the positive electrode of wide material sources becomes the further important technology direction of improving the Rechargeable zinc ion battery performance.
Summary of the invention
The purpose of this invention is to provide a kind of aqueous solution electrolysis liquid Rechargeable zinc ion battery.
A kind of aqueous solution electrolysis liquid Rechargeable zinc ion battery, this battery is by positive pole, negative pole, between the diaphragm material between the above two and electrolyte ingredient with ionic conductivity; Wherein positive pole comprises the positive electrode active materials on collector and the collector, and negative pole comprises the negative active core-shell material on collector and the collector; Positive electrode active materials is KMFe (CN)
6The film material that powder, electronic conductor and binding agent are made; Negative active core-shell material is the film material that zinc powder, corrosion inhibiter, electronic conductor and binding agent are made; Electrolyte for take the soluble-salt of zinc as solute, water is the liquid state with ionic conductivity or the gel state material of solvent, its pH value is in 4 ~ 7.
KMFe (CN)
6In M be Cu or Ni element.
The addition of electronic conductor, binding agent is respectively below 10% of positive electrode active materials quality in the positive electrode active materials.
The addition of corrosion inhibiter is below 1% of negative active core-shell material quality in the negative active core-shell material, and the addition of electronic conductor, binding agent is respectively below 10% of negative active core-shell material quality.
Above-mentioned electrodes conduct agent is graphite, carbon black, acetylene black, carbon nano-fiber or carbon nano-tube.
Above-mentioned corrosion inhibiter is oxide or hydroxide or the copper of indium.
Above-mentioned binding agent is polytetrafluoroethylene, poly-inclined to one side tetrafluoroethene or cellulose.
The soluble-salt of above-mentioned zinc is zinc nitrate, zinc sulfate or zinc chloride.
The Rechargeable zinc ion battery that the present invention proposes, its battery structure can be button, column type or square structure.
Beneficial effect of the present invention is: 1) adopt the zinc metal as battery cathode, its activity is high, cheap, be easy to get, and is pollution-free; 2) utilize that the insoluble iron cyanide is cheap as positive electrode, preparation technology is simple; 3) adopt contain zinc ion the aqueous solution as electrolyte, prepare simple and easy, do not fire, nontoxic; 4) Rechargeable zinc ion battery of the present invention, utilize zinc ion in the positive electrode lattice reversible embedding or deviate from, carry out simultaneously oxidation or zinc ion take the zinc element as main negative material in the energy storage mechanism of negative terminal surface reduction, and adopted special electrolyte, this battery has the characteristics of specific capacity height and quickly-chargeable, and it has the advantages such as manufacturing process is simple, cost is low, have extended cycle life simultaneously.
Description of drawings
Fig. 1 is that iron copper cyanider electrode is at 1mol L
-1ZnSO
4The cyclic voltammogram of electrolyte.
Fig. 2 is that Rechargeable zinc ion battery is at 200 mAg
-1The charging and discharging curve first time under the current density.
Fig. 3 is Rechargeable zinc ion battery at 200 mAg
-1Cycle charge-discharge curve under the current density.
Fig. 4 is Rechargeable zinc ion battery at 150 mAg
-1Charging and discharging curve under the current density.
Embodiment
Embodiment 1
Iron copper cyanider KCuFe (CN)
6Preparation
The potassium ferricyanide solution of certain density copper sulphate (copper chloride, zinc sulfate, zinc chloride, nickelous sulfate, nickel chloride etc.) solution and same concentrations is dropwise splashed in the deionized water of continuous stirring simultaneously, after question response is complete, with the suspension-turbid liquid that is mixed with brown precipitate through ultrasonic oscillation after 30 minutes, left standstill 8 hours, then sediment is leached, and after repeatedly cleaning with deionized water, put into baking oven and dry, make iron copper cyanider powder.
Be coated on the carbon element collector after the poly-inclined to one side tetrafluoroethene of iron copper cyanider, electronic conductor graphite powder and binding agent mixed with the mass ratio of 18:1:1, be cut into a certain size, make iron copper cyanider electrode slice in oven for drying.It is work electrode that iron copper cyanider electrode slice is adopted in the single electrode test, take the metal platinum electrode as auxiliary electrode, detects as reference electrode with saturated calomel electrode.Iron copper cyanider electrode is at 1mol L
-1ZnSO
4Cyclic voltammogram in the aqueous solution as shown in Figure 1, sweep speed is 10mV s
-1, can find out has an oxidation peak and reduction peak to occur, corresponding to zinc ion deviating from and embed in iron copper cyanider lattice.
Embodiment 2
Be coated on the carbon element collector after the poly-inclined to one side tetrafluoroethene of zinc powder, electronic conductor graphite powder and binding agent mixed with the mass ratio of 18:1:1, be cut into a certain size, make zinc electrode in oven for drying.Take the iron copper cyanider electrode of embodiment 1 preparation as anodal, take zinc electrode as negative pole, electrolyte is 1mol L
-1ZnSO
4The aqueous solution is assembled into the Rechargeable zinc ion battery of flexible package.
Prepared Zinc ion battery is at 200 mAg
-1Constant current for the first time charging and discharging curve is seen Fig. 2 (with the positive electrode active materials Mass Calculation), as shown in the figure, between voltage range 2.0 ~ 2.2V, a charging platform occurred, and a discharge platform is clearly arranged about 0.75V, and enclosed pasture efficient is 81%.Prepared Zinc ion battery is at 200 mAg
-1Constant current charge-discharge cyclic curve (with the positive electrode active materials Mass Calculation) as shown in Figure 3, as seen from the figure, made Zinc ion battery has preferably cycle characteristics.If through structure optimization, this battery charging and discharging characteristic and cyclical stability also will have obvious lifting.
Embodiment 3
Be coated on the carbon element collector after the poly-inclined to one side tetrafluoroethene of zinc powder, conductive agent graphite powder, binding agent and corrosion inhibiter copper powder mixed with the mass ratio of 83:8:8:1, in oven for drying, be cut into a certain size, make zinc electrode.Take the iron copper cyanider electrode of embodiment 1 preparation as anodal, take zinc electrode as negative pole, electrolyte is 1mol L
-1ZnSO
4The aqueous solution is assembled into the Rechargeable zinc ion battery of flexible package.Prepared Zinc ion battery is at 150 mA g
-1Constant current charge-discharge curve (with the positive electrode active materials Mass Calculation) is seen Fig. 4, as shown in the figure, between voltage range 2.1 ~ 2.2V, a charging platform occurred, and a discharge platform is clearly arranged about 0.75V, and enclosed pasture efficient is 78%.If through structure optimization, this battery charging and discharging characteristic and cyclical stability also will have obvious lifting.
Claims (8)
1. aqueous solution electrolysis liquid Rechargeable zinc ion battery, this battery are by positive pole, negative pole, form between the diaphragm material between the above two and electrolyte; Wherein positive pole comprises the positive electrode active materials on collector and the collector, and negative pole comprises the negative active core-shell material on collector and the collector, it is characterized in that, positive electrode active materials is KMFe (CN)
6The film material that powder, electronic conductor and binding agent are made; Negative active core-shell material is the film material that zinc powder, corrosion inhibiter, electronic conductor and binding agent are made; Electrolyte for take the soluble-salt of zinc as solute, water is the liquid state with ionic conductivity or the gel state material of solvent, its pH value is in 4 ~ 7.
2. electrolyte Rechargeable zinc ion battery according to claim 1 is characterized in that, described KMFe (CN)
6In M be Cu or Ni element.
3. electrolyte Rechargeable zinc ion battery according to claim 1 is characterized in that, the addition of electronic conductor, binding agent is respectively below 10% of positive electrode active materials quality in the positive electrode active materials.
4. electrolyte Rechargeable zinc ion battery according to claim 1, it is characterized in that, the addition of corrosion inhibiter is below 1% of negative active core-shell material quality in the negative active core-shell material, and the addition of electronic conductor, binding agent is respectively below 10% of negative active core-shell material quality.
5. electrolyte Rechargeable zinc ion battery according to claim 1 is characterized in that, described electronic conductor is graphite, carbon black, acetylene black, carbon nano-fiber or carbon nano-tube.
6. electrolyte Rechargeable zinc ion battery according to claim 1 is characterized in that, described corrosion inhibiter is oxide or hydroxide or the copper of indium.
7. electrolyte Rechargeable zinc ion battery according to claim 1 is characterized in that, described binding agent is polytetrafluoroethylene, poly-inclined to one side tetrafluoroethene or cellulose.
8. electrolyte Rechargeable zinc ion battery according to claim 1 is characterized in that, the soluble-salt of described zinc is zinc nitrate, zinc sulfate or zinc chloride.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210380142.6A CN102903917B (en) | 2012-10-09 | 2012-10-09 | Aqueous electrolyte rechargeable zinc ion battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210380142.6A CN102903917B (en) | 2012-10-09 | 2012-10-09 | Aqueous electrolyte rechargeable zinc ion battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102903917A true CN102903917A (en) | 2013-01-30 |
| CN102903917B CN102903917B (en) | 2015-04-15 |
Family
ID=47576057
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210380142.6A Expired - Fee Related CN102903917B (en) | 2012-10-09 | 2012-10-09 | Aqueous electrolyte rechargeable zinc ion battery |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102903917B (en) |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103972582A (en) * | 2014-05-27 | 2014-08-06 | 中国科学院宁波材料技术与工程研究所 | Secondary battery |
| CN103972479A (en) * | 2014-05-27 | 2014-08-06 | 中国科学院宁波材料技术与工程研究所 | Ion battery |
| WO2015193787A1 (en) | 2014-06-16 | 2015-12-23 | Torre Pasquale | Rechargeable battery containing zinc ions |
| CN107516735A (en) * | 2017-08-21 | 2017-12-26 | 湖南科技大学 | A kind of secondary iron base composite material iron copper cyanider battery and its manufacture method |
| CN108448168A (en) * | 2018-03-14 | 2018-08-24 | 华中科技大学 | A kind of electrolyte and its preparation method and application for water system zinc ion secondary cell |
| CN108847476A (en) * | 2018-06-07 | 2018-11-20 | 哈尔滨工业大学（威海） | Preparation method of zinc ion battery anode |
| CN109643785A (en) * | 2016-08-24 | 2019-04-16 | Dst创新有限公司 | Rechargeable cell |
| CN109728295A (en) * | 2017-10-30 | 2019-05-07 | 宁德时代新能源科技股份有限公司 | Positive active material, preparation method thereof and sodium ion battery |
| CN110364771A (en) * | 2018-04-10 | 2019-10-22 | 中国科学院上海硅酸盐研究所 | A kind of water system zinc ion soft-package battery and preparation method thereof |
| CN110364692A (en) * | 2018-04-10 | 2019-10-22 | 中国科学院上海硅酸盐研究所 | Composite zinc cathode with multiphase material |
| CN111653788A (en) * | 2020-07-14 | 2020-09-11 | 无锡永华电池有限公司 | Alkaline battery negative electrode material |
| CN112164802A (en) * | 2020-09-30 | 2021-01-01 | 国网上海市电力公司 | Application of metal material and zinc-based battery taking metal as negative electrode |
| CN113097518A (en) * | 2021-03-18 | 2021-07-09 | 苏州柔能纳米科技有限公司 | Electrolyte for flexible neutral zinc-manganese dioxide battery and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20020182499A1 (en) * | 2001-04-19 | 2002-12-05 | Michael Cheiky | Battery separator with copper-containing inorganic salt |
| CN102097661A (en) * | 2009-12-11 | 2011-06-15 | 清华大学深圳研究生院 | Rechargeable zinc ion battery using zinc manganate as anode |
| JP2012046399A (en) * | 2010-08-30 | 2012-03-08 | National Institute Of Advanced Industrial Science & Technology | Electrode material for lithium ion secondary battery using non-defective prussian blue analogue |
| CN102522553A (en) * | 2011-12-31 | 2012-06-27 | 武汉大学 | Sodium ion battery positive material |
-
2012
- 2012-10-09 CN CN201210380142.6A patent/CN102903917B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20020182499A1 (en) * | 2001-04-19 | 2002-12-05 | Michael Cheiky | Battery separator with copper-containing inorganic salt |
| CN102097661A (en) * | 2009-12-11 | 2011-06-15 | 清华大学深圳研究生院 | Rechargeable zinc ion battery using zinc manganate as anode |
| JP2012046399A (en) * | 2010-08-30 | 2012-03-08 | National Institute Of Advanced Industrial Science & Technology | Electrode material for lithium ion secondary battery using non-defective prussian blue analogue |
| CN102522553A (en) * | 2011-12-31 | 2012-06-27 | 武汉大学 | Sodium ion battery positive material |
Non-Patent Citations (2)
| Title |
|---|
| N. IMANISHI ET AL.: "Lithium intercalation behavior into iron cyanide complex as positive electrode of lithium secondary battery", 《JOURNAL OF POWER SOURCES》, no. 79, 31 December 1999 (1999-12-31), pages 215 - 219 * |
| N. IMANISHI ET AL.: "Lithium intercalation behavior of iron cyanometallates", 《JOURNAL OF POWER SOURCES》, no. 8182, 31 December 1999 (1999-12-31), pages 530 - 534 * |
Cited By (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103972582A (en) * | 2014-05-27 | 2014-08-06 | 中国科学院宁波材料技术与工程研究所 | Secondary battery |
| CN103972479A (en) * | 2014-05-27 | 2014-08-06 | 中国科学院宁波材料技术与工程研究所 | Ion battery |
| CN103972582B (en) * | 2014-05-27 | 2016-03-30 | 中国科学院宁波材料技术与工程研究所 | A kind of secondary cell |
| WO2015193787A1 (en) | 2014-06-16 | 2015-12-23 | Torre Pasquale | Rechargeable battery containing zinc ions |
| CN106575758A (en) * | 2014-06-16 | 2017-04-19 | 特斯博有限责任公司 | Rechargeable battery containing zinc ions |
| JP2017523563A (en) * | 2014-06-16 | 2017-08-17 | ティーティーエスビー エス．アール．エル． | Rechargeable battery containing lead ion |
| US11201360B2 (en) | 2016-08-24 | 2021-12-14 | Dst Innovations Limited | Rechargeable power cells |
| CN109643785A (en) * | 2016-08-24 | 2019-04-16 | Dst创新有限公司 | Rechargeable cell |
| CN107516735A (en) * | 2017-08-21 | 2017-12-26 | 湖南科技大学 | A kind of secondary iron base composite material iron copper cyanider battery and its manufacture method |
| CN107516735B (en) * | 2017-08-21 | 2019-08-23 | 湖南科技大学 | A kind of secondary iron base composite material-iron copper cyanider battery and its manufacturing method |
| CN109728295A (en) * | 2017-10-30 | 2019-05-07 | 宁德时代新能源科技股份有限公司 | Positive active material, preparation method thereof and sodium ion battery |
| CN108448168A (en) * | 2018-03-14 | 2018-08-24 | 华中科技大学 | A kind of electrolyte and its preparation method and application for water system zinc ion secondary cell |
| CN110364771A (en) * | 2018-04-10 | 2019-10-22 | 中国科学院上海硅酸盐研究所 | A kind of water system zinc ion soft-package battery and preparation method thereof |
| CN110364692A (en) * | 2018-04-10 | 2019-10-22 | 中国科学院上海硅酸盐研究所 | Composite zinc cathode with multiphase material |
| CN108847476A (en) * | 2018-06-07 | 2018-11-20 | 哈尔滨工业大学（威海） | Preparation method of zinc ion battery anode |
| CN111653788A (en) * | 2020-07-14 | 2020-09-11 | 无锡永华电池有限公司 | Alkaline battery negative electrode material |
| CN112164802A (en) * | 2020-09-30 | 2021-01-01 | 国网上海市电力公司 | Application of metal material and zinc-based battery taking metal as negative electrode |
| CN113097518A (en) * | 2021-03-18 | 2021-07-09 | 苏州柔能纳米科技有限公司 | Electrolyte for flexible neutral zinc-manganese dioxide battery and preparation method thereof |
| CN113097518B (en) * | 2021-03-18 | 2024-06-04 | 苏州柔能纳米科技有限公司 | Electrolyte for flexible neutral zinc-manganese battery and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102903917B (en) | 2015-04-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102903917B (en) | Aqueous electrolyte rechargeable zinc ion battery | |
| CN102013527B (en) | Rechargeable zinc ion battery | |
| CN105609754B (en) | A kind of double positive electrodes and aqoue seconary battery | |
| CN102110858B (en) | Chargeable zinc ion battery by taking oxide of vanadium as cathode | |
| CN105958131B (en) | Rechargeable aqueous zinc ion battery with long cycle life and high energy density | |
| CN105047932B (en) | A kind of aquo-lithium ion battery quinones negative material and aquo-lithium ion battery | |
| CN105826520A (en) | Water system high-voltage mixed ion secondary battery based on zinc-lithium ferric manganese phosphate | |
| CN102683757B (en) | High-capacity rechargeable zinc ion battery | |
| CN102005615B (en) | Rechargeable nickel ion battery | |
| CN104779394A (en) | Aqueous lithium (sodium) ion battery mixed negative material | |
| CN104795567B (en) | Aquo-lithium ion/sodium-ion battery based on iodide ion solution anode and organic matter cathode | |
| CN107180966A (en) | A kind of new aqoue seconary battery using lithium salts and sodium salt as electrode material | |
| KR20140039022A (en) | Battery | |
| CN103441260B (en) | A kind of aqueous alkaline electrochemical energy storing device | |
| CN103219551A (en) | Water-system alkali metal ion power storage device | |
| CN101221853A (en) | Semi-solid state or full-solid state water system super capacitor | |
| CN104362393A (en) | Rechargeable aqueous ion battery | |
| CN103441259A (en) | Anode material of high-magnification aqueous alkali metal electrochemical battery and preparation method of anode material | |
| CN104716372A (en) | Aqueous lithium ion flow battery | |
| CN104167540A (en) | Negative electrode active material and preparation method thereof and lithium ion battery | |
| CN104347894A (en) | A sedimentary type aqueous lithium ion battery | |
| CN103682303B (en) | Lithium ion battery anode active material and preparation method thereof and lithium ion battery | |
| CN104064824A (en) | Water system rechargeable battery | |
| CN101262056A (en) | A water solution chargeable lithium ion battery | |
| CN105489949B (en) | A kind of mixed aqueous solution battery preparation method based on embedding sodium positive electrode |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20150415 Termination date: 20181009 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |