CN102683756A - Polymer rechargeable zinc ion battery - Google Patents
Polymer rechargeable zinc ion battery Download PDFInfo
- Publication number
- CN102683756A CN102683756A CN2011100619906A CN201110061990A CN102683756A CN 102683756 A CN102683756 A CN 102683756A CN 2011100619906 A CN2011100619906 A CN 2011100619906A CN 201110061990 A CN201110061990 A CN 201110061990A CN 102683756 A CN102683756 A CN 102683756A
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- CN
- China
- Prior art keywords
- zinc
- ion battery
- zinc ion
- battery according
- electrolyte
- 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.)
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- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 229920000642 polymer Polymers 0.000 title claims abstract description 12
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000011701 zinc Substances 0.000 claims abstract description 18
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 18
- 239000003792 electrolyte Substances 0.000 claims abstract description 16
- 239000000463 material Substances 0.000 claims abstract description 10
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000011230 binding agent Substances 0.000 claims description 9
- 239000001913 cellulose Substances 0.000 claims description 8
- 229920002678 cellulose Polymers 0.000 claims description 8
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 7
- 229920002401 polyacrylamide Polymers 0.000 claims description 7
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 239000011149 active material Substances 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 6
- 239000000499 gel Substances 0.000 claims description 5
- 239000011258 core-shell material Substances 0.000 claims description 4
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical compound FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 4
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 4
- 229960001763 zinc sulfate Drugs 0.000 claims description 4
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 4
- -1 polytetrafluoroethylene Polymers 0.000 claims description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 3
- 239000007774 positive electrode material Substances 0.000 claims description 3
- 108010010803 Gelatin Proteins 0.000 claims description 2
- 229910045601 alloy Inorganic materials 0.000 claims description 2
- 239000000956 alloy Substances 0.000 claims description 2
- 230000004888 barrier function Effects 0.000 claims description 2
- 239000008273 gelatin Substances 0.000 claims description 2
- 229920000159 gelatin Polymers 0.000 claims description 2
- 235000019322 gelatine Nutrition 0.000 claims description 2
- 235000011852 gelatine desserts Nutrition 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 235000005074 zinc chloride Nutrition 0.000 claims description 2
- 239000011592 zinc chloride Substances 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 abstract description 2
- 239000013543 active substance Substances 0.000 abstract 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
- 238000007599 discharging Methods 0.000 description 6
- 239000006230 acetylene black Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- 229920000609 methyl cellulose Polymers 0.000 description 3
- 239000001923 methylcellulose Substances 0.000 description 3
- 235000010981 methylcellulose Nutrition 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 239000001856 Ethyl cellulose Substances 0.000 description 2
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000002041 carbon nanotube Substances 0.000 description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 description 2
- 239000003610 charcoal Substances 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 229920001249 ethyl cellulose Polymers 0.000 description 2
- 235000019325 ethyl cellulose Nutrition 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- LNAZSHAWQACDHT-XIYTZBAFSA-N (2r,3r,4s,5r,6s)-4,5-dimethoxy-2-(methoxymethyl)-3-[(2s,3r,4s,5r,6r)-3,4,5-trimethoxy-6-(methoxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6r)-4,5,6-trimethoxy-2-(methoxymethyl)oxan-3-yl]oxyoxane Chemical compound CO[C@@H]1[C@@H](OC)[C@H](OC)[C@@H](COC)O[C@H]1O[C@H]1[C@H](OC)[C@@H](OC)[C@H](O[C@H]2[C@@H]([C@@H](OC)[C@H](OC)O[C@@H]2COC)OC)O[C@@H]1COC LNAZSHAWQACDHT-XIYTZBAFSA-N 0.000 description 1
- AHLWZBVXSWOPPL-RGYGYFBISA-N 20-deoxy-20-oxophorbol 12-myristate 13-acetate Chemical compound C([C@]1(O)C(=O)C(C)=C[C@H]1[C@@]1(O)[C@H](C)[C@H]2OC(=O)CCCCCCCCCCCCC)C(C=O)=C[C@H]1[C@H]1[C@]2(OC(C)=O)C1(C)C AHLWZBVXSWOPPL-RGYGYFBISA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 241001602688 Pama Species 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
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
Abstract
Provided is a polymer rechargeable zinc ion battery. The positive electrode uses manganese dioxide as the main materials, the negative electrode uses zinc element as the main materials, and soluble salt with zinc as the electrolyte is directly dissolved and suspended in tremellose high polymers. The polymer rechargeable zinc ion battery has the advantages of being not apt to weep, long in storing time, high in utilization rate of active substances and the like.
Description
Technical field
The invention belongs to the battery technology field, be specifically related to the chargeable Zinc ion battery of a kind of polymer.
Background technology
The primary cell of comparing, secondary cell can repeat repeatedly to carry out charge and discharge cycles, can make full use of raw material, so its more economical practicality, secondary cell also can greatly be alleviated the pollution that is brought by discarded primary cell simultaneously.
Existing chargeable Zinc ion battery is to use the aqueous solution of zinc soluble-salt to be electrolyte, yet it is higher to the sealing requirements of battery to use the aqueous solution to do electrolyte, if water outlet leakage and oxidizing and crystallizing can take place when battery sealing-performance is relatively poor, causes battery performance decline.
Summary of the invention
Technical problem to be solved by this invention is that existing chargeable Zinc ion battery is higher to sealing requirements, leakage and oxidizing and crystallizing take place easily and causes battery performance decline.
For this reason; The present invention proposes the chargeable Zinc ion battery of a kind of polymer; It is made up of positive pole, negative pole, marginal barrier film and the electrolyte that contains zwitterion and have an ionic conductivity, and wherein, it is main active material that said negative pole adopts with the zinc element; Positive electrode active materials is a manganese dioxide, and said electrolyte is that the soluble-salt with zinc directly dissolves, is suspended in the gel state material in the gelatin high molecular polymer.
Said high molecular polymer preferably adopts cellulose family thing, polyacrylamide thing and high-molecular polyvinyl alcohol material.Wherein, cellulose family thing preferable methyl cellulose, ethyl cellulose, carboxymethyl cellulose etc., the polyacrylamide thing can be selected one or more nonionic, anion, cation or amphiprotic polyacrylamide.
The preferred following electrolyte of said electrolyte: in mass, electrolyte is made up of 0.2%～5% cellulose family thing, 0.01%～0.05% polyvinyl alcohol, 0.1%～0.3% polyacrylamide thing, the soluble-salt of 25%～40% zinc and the water of surplus.
The soluble-salt of said zinc can adopt the inorganic salts of zinc such as zinc nitrate, zinc sulfate or zinc chloride.
Said negative pole can be the alloy of simple metal zinc or zinc.
Said negative pole can also adopt following structure: negative pole comprises on collector and the collector being main active material with the zinc powder, and this active material is the film material of processing with zinc powder and binding agent.Further, also can in negative active core-shell material, add the electron conduction agent, the electron conduction agent can be adopted graphite, carbon black, acetylene black, charcoal fiber or carbon nanotube, and addition is below 50% of negative electrode film quality.Binding agent in the negative active core-shell material can adopt polytetrafluoroethylene, water-soluble rubber, gather inclined to one side tetrafluoroethene or cellulose, and addition is preferably below 50% of negative electrode film quality.
Positive pole also comprises electron conduction agent and binding agent except said positive electrode active materials, wherein, the electron conduction agent can be graphite, carbon black, acetylene black, charcoal fiber or carbon nanotube, and addition is below 50% of cathode film quality; Binding agent can be for polytetrafluoroethylene, water-soluble rubber, gather inclined to one side tetrafluoroethene or cellulose, and addition is below 20% of cathode film quality.
The chargeable Zinc ion battery of the present invention is owing to adopt high-viscosity gel attitude electrolyte, and is mobile less, so can the water outlet leakage; Simultaneously; The gel state material density is bigger, and airtight effect is strong, is difficult for dehydration; Be difficult for the occurrence of large-area oxidizing and crystallizing, so the chargeable Zinc ion battery of the present invention have not easy-to-leak liquid, long characteristics of storage time.On the other hand, because electrolyte adopts the gel state material, can reduce the airtight requirement of battery, thereby can simplify the production technology of battery.
Description of drawings
The battery Cell 1 that Fig. 1 makes for embodiment 1 is at 100 mA g
-1Charging and discharging curve under the constant current.
The battery Cell 2 that Fig. 2 makes for embodiment 2 is at 100 mA g
-1Charging and discharging curve under the constant current.
The battery Cell 3 that Fig. 3 makes for embodiment 3 is at 100 mA g
-1Charging and discharging curve under the constant current.
Embodiment
Below in conjunction with embodiment and accompanying drawing the present invention is further specified.
Embodiment 1:
Be coated on the stainless steel foil after manganese dioxide, conductive agent acetylene black and binding agent PVDF (gathering inclined to one side tetrafluoroethene) mixed by mass ratio 7:2:1, be cut into a certain size, oven dry makes electrode slice 1 in vacuum.With electrode slice 1 is positive pole; With the thick zinc paper tinsel of 0.1mm is negative pole; The concrete quality proportioning of electrolyte is: methylcellulose 0.2%, polyvinyl alcohol 0.01%, molecular weight are that 10,000 PAMA 0.1%, zinc sulfate 25%, surplus are water; Be assembled into chargeable Zinc ion battery, be designated as Cell 1.Through test, Cell 1 is at 100 mA g
-1Charging and discharging curve under the constant current is seen Fig. 1.
Embodiment 2:
The electrode slice 1 that makes with embodiment 1 is a positive pole; With the thick zinc paper tinsel of 0.1mm is negative pole; The concrete quality proportioning of electrolyte is: ethyl cellulose 5%, polyvinyl alcohol 0.05%, molecular weight are that 5,000 PAMC 0.3%, zinc nitrate 40%, surplus are water; Be assembled into chargeable Zinc ion battery, be designated as Cell 2.Through test, Cell 2 is at 100 mA g
-1Charging and discharging curve under the constant current is seen Fig. 2.
Embodiment 3:
Be coated on the stainless steel foil after zinc powder, conductive agent acetylene black and binding agent PVDF mixed by mass ratio 8:1:1, be cut into a certain size, oven dry makes electrode slice 2 in vacuum.The electrode slice 1 that makes with embodiment 1 is a positive pole; With electrode slice 2 is negative pole; The concrete weight proportion of electrolyte is: methylcellulose 3%, polyvinyl alcohol 0.03%, molecular weight are that 30,000 non-ionic polyacrylamide 0.2%, zinc sulfate 30%, surplus are water; Be assembled into chargeable Zinc ion battery, be designated as Cell 3.Through test, Cell 3 is at 100 mA g
-1Charging and discharging curve under the constant current is seen Fig. 3.
Claims (8)
1. chargeable Zinc ion battery of polymer; Form by positive pole, negative pole, marginal barrier film and the electrolyte that contains zwitterion and have an ionic conductivity; It is characterized in that: it is main active material that said negative pole adopts with the zinc element; Positive electrode active materials is a manganese dioxide, and said electrolyte is that the soluble-salt with zinc directly dissolves, is suspended in the gel state material in the gelatin high molecular polymer.
2. Zinc ion battery according to claim 1 is characterized in that: said high molecular polymer is cellulose family thing, polyacrylamide thing and high-molecular polyvinyl alcohol material.
3. Zinc ion battery according to claim 2 is characterized in that: said in mass electrolyte is made up of 0.2%～5% cellulose family thing, 0.01%～0.05% polyvinyl alcohol, 0.1%～0.3% polyacrylamide thing, the soluble-salt of 25%～40% zinc and the water of surplus.
4. according to each described Zinc ion battery of claim 1-3, it is characterized in that: the soluble-salt of said zinc is zinc nitrate, zinc sulfate or zinc chloride.
5. Zinc ion battery according to claim 4 is characterized in that: said negative pole is the alloy of simple metal zinc or zinc.
6. Zinc ion battery according to claim 4 is characterized in that: said negative pole comprises on collector and the collector being main active material with the zinc powder, and this active material is the film material of processing with zinc powder and binding agent.
7. Zinc ion battery according to claim 6 is characterized in that: comprise also in the negative active core-shell material that electron conduction agent, the addition of electron conduction agent are below 50% of negative electrode film quality.
8. chargeable zinc ion battery according to claim 7 is characterized in that: the binding agent in the negative active core-shell material is polytetrafluoroethylene, water-soluble rubber, gathers inclined to one side tetrafluoroethene or cellulose that the addition of binding agent is below 50% of negative electrode film quality.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110061990.6A CN102683756B (en) | 2011-03-15 | 2011-03-15 | Polymer rechargeable zinc ion battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110061990.6A CN102683756B (en) | 2011-03-15 | 2011-03-15 | Polymer rechargeable zinc ion battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102683756A true CN102683756A (en) | 2012-09-19 |
| CN102683756B CN102683756B (en) | 2014-10-22 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201110061990.6A Active CN102683756B (en) | 2011-03-15 | 2011-03-15 | Polymer rechargeable zinc ion battery |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102683756B (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016154885A1 (en) * | 2015-03-31 | 2016-10-06 | 深圳市寒暑科技新能源有限公司 | Method for manufacturing electrode of a zinc ion battery and rechargeable battery based on same |
| CN111525185A (en) * | 2020-03-30 | 2020-08-11 | 东华大学 | Flexible zinc ion battery polymer electrolyte and preparation and application thereof |
| CN112768750A (en) * | 2021-01-20 | 2021-05-07 | 南京林业大学 | Recyclable zinc bromide-based solid energy storage electrolyte, and preparation method and application thereof |
| CN113078371A (en) * | 2021-03-25 | 2021-07-06 | 郑州大学 | Aqueous zinc ion battery electrolyte and preparation method and application thereof |
| CN114388903A (en) * | 2022-01-11 | 2022-04-22 | 河南科技大学 | Organic additive-containing electrolyte for water-based zinc ion battery, preparation method of organic additive-containing electrolyte and water-based zinc ion battery |
| CN114551845A (en) * | 2022-03-02 | 2022-05-27 | 成都理工大学 | Zinc ion battery with self-charging characteristic and preparation method thereof |
| CN114597387A (en) * | 2022-03-11 | 2022-06-07 | 广东工业大学 | Zinc metal negative electrode material and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1151087A (en) * | 1995-11-21 | 1997-06-04 | 杨建生 | High-efficiency zinc-manganese battery |
| CN101783419A (en) * | 2009-01-16 | 2010-07-21 | 清华大学深圳研究生院 | Rechargeable zinc ion battery |
-
2011
- 2011-03-15 CN CN201110061990.6A patent/CN102683756B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1151087A (en) * | 1995-11-21 | 1997-06-04 | 杨建生 | High-efficiency zinc-manganese battery |
| CN101783419A (en) * | 2009-01-16 | 2010-07-21 | 清华大学深圳研究生院 | Rechargeable zinc ion battery |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016154885A1 (en) * | 2015-03-31 | 2016-10-06 | 深圳市寒暑科技新能源有限公司 | Method for manufacturing electrode of a zinc ion battery and rechargeable battery based on same |
| CN111525185A (en) * | 2020-03-30 | 2020-08-11 | 东华大学 | Flexible zinc ion battery polymer electrolyte and preparation and application thereof |
| CN112768750A (en) * | 2021-01-20 | 2021-05-07 | 南京林业大学 | Recyclable zinc bromide-based solid energy storage electrolyte, and preparation method and application thereof |
| CN113078371A (en) * | 2021-03-25 | 2021-07-06 | 郑州大学 | Aqueous zinc ion battery electrolyte and preparation method and application thereof |
| CN114388903A (en) * | 2022-01-11 | 2022-04-22 | 河南科技大学 | Organic additive-containing electrolyte for water-based zinc ion battery, preparation method of organic additive-containing electrolyte and water-based zinc ion battery |
| CN114388903B (en) * | 2022-01-11 | 2023-11-07 | 河南科技大学 | Electrolyte containing organic additive for water-based zinc ion battery, preparation method of electrolyte and water-based zinc ion battery |
| CN114551845A (en) * | 2022-03-02 | 2022-05-27 | 成都理工大学 | Zinc ion battery with self-charging characteristic and preparation method thereof |
| CN114597387A (en) * | 2022-03-11 | 2022-06-07 | 广东工业大学 | Zinc metal negative electrode material and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102683756B (en) | 2014-10-22 |
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Address after: Room 401, Unit 1, Building 1, Xinchen New Materials Pilot Industrialization Base, No. 300, Shutianpu Road, Shutianpu Community, Matian Street, Guangming District, Shenzhen, Guangdong Province, 518000 Patentee after: SHENZHEN CUBIC-SCIENCE Co.,Ltd. Address before: 518040 085, 2nd Floor, Tairan Yunsong Building, Binhe Road, Futian District, Shenzhen City, Guangdong Province Patentee before: SHENZHEN CUBIC-SCIENCE Co.,Ltd. |