CN112242571A - Electrolyte for protecting zinc ion battery electrode and zinc ion battery - Google Patents
Electrolyte for protecting zinc ion battery electrode and zinc ion battery Download PDFInfo
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- CN112242571A CN112242571A CN202011109262.3A CN202011109262A CN112242571A CN 112242571 A CN112242571 A CN 112242571A CN 202011109262 A CN202011109262 A CN 202011109262A CN 112242571 A CN112242571 A CN 112242571A
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- Prior art keywords
- zinc
- ion battery
- electrolyte
- zinc ion
- electrode
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- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 239000003792 electrolyte Substances 0.000 title claims abstract description 37
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 37
- 239000011701 zinc Substances 0.000 claims abstract description 34
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 34
- 239000005543 nano-size silicon particle Substances 0.000 claims abstract description 14
- 150000003751 zinc Chemical class 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000008367 deionised water Substances 0.000 claims abstract description 4
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 4
- 239000000463 material Substances 0.000 claims description 9
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 7
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 6
- BHHYHSUAOQUXJK-UHFFFAOYSA-L zinc fluoride Chemical compound F[Zn]F BHHYHSUAOQUXJK-UHFFFAOYSA-L 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
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 5
- 229960001763 zinc sulfate Drugs 0.000 claims description 5
- 239000011149 active material Substances 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 3
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 3
- 239000011230 binding agent Substances 0.000 claims description 3
- 239000006258 conductive agent Substances 0.000 claims description 3
- 239000003365 glass fiber Substances 0.000 claims description 3
- 229910052748 manganese Inorganic materials 0.000 claims description 3
- 239000011572 manganese Substances 0.000 claims description 3
- 229960003351 prussian blue Drugs 0.000 claims description 3
- 239000013225 prussian blue Substances 0.000 claims description 3
- 229910052720 vanadium Inorganic materials 0.000 claims description 3
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 3
- 239000004246 zinc acetate Substances 0.000 claims description 3
- 239000011592 zinc chloride Substances 0.000 claims description 3
- 235000005074 zinc chloride Nutrition 0.000 claims description 3
- ZMLPZCGHASSGEA-UHFFFAOYSA-M zinc trifluoromethanesulfonate Chemical compound [Zn+2].[O-]S(=O)(=O)C(F)(F)F ZMLPZCGHASSGEA-UHFFFAOYSA-M 0.000 claims description 3
- CITILBVTAYEWKR-UHFFFAOYSA-L zinc trifluoromethanesulfonate Substances [Zn+2].[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F CITILBVTAYEWKR-UHFFFAOYSA-L 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 2
- 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 claims description 2
- 210000001787 dendrite Anatomy 0.000 abstract description 8
- 238000002360 preparation method Methods 0.000 abstract description 5
- 238000000840 electrochemical analysis Methods 0.000 abstract description 3
- 238000000034 method Methods 0.000 abstract description 3
- 230000002035 prolonged effect Effects 0.000 abstract description 2
- 210000004027 cell Anatomy 0.000 description 7
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 6
- 229910001416 lithium ion Inorganic materials 0.000 description 6
- 230000001351 cycling effect Effects 0.000 description 5
- -1 zinc hexafluoro-silicate Chemical compound 0.000 description 3
- 239000013543 active substance Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- 238000000635 electron micrograph Methods 0.000 description 2
- 239000011686 zinc sulphate Substances 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Images
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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0002—Aqueous electrolytes
- H01M2300/0005—Acid electrolytes
-
- 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
Abstract
The invention discloses an electrolyte for protecting a zinc ion battery electrode and a zinc ion battery, wherein the electrolyte comprises soluble zinc salt, silicon nanoparticles and deionized water, wherein the concentration of the soluble zinc salt is 0.1-10 mol/L, and the concentration of the silicon nanoparticles is 0.01-10 g/L. According to the invention, silicon nanoparticles are introduced into the electrolyte, and the growth of zinc dendrites is realized in the circulation process, so that the electrode of the zinc ion battery is protected, and the circulation life of the zinc ion battery is obviously prolonged. The electrolyte disclosed by the invention is simple in preparation formula and simple in preparation process operation, and the electrical cycle life and the cycle stability of the zinc ion battery prepared by using the electrolyte are effectively improved through electrochemical tests.
Description
Technical Field
The invention belongs to the technical field of zinc ion batteries, and particularly relates to electrolyte for protecting a zinc ion battery electrode and a zinc ion battery.
Background
Lithium ion batteries have enjoyed great success in portable electronic devices and have begun to emerge in the forefront of the way in large-scale energy storage such as electric vehicles. However, with the continuous pursuit of high energy density, high capacity and low cost, the defects of the lithium ion battery are gradually exposed. Firstly, in the aspect of safety, unstable lithium ions and organic electrolyte can easily cause the battery to be on fire or even explode, so that high potential safety hazards exist, and the cost of the lithium ion battery is very high due to harsh production conditions. In addition, the recovery and treatment of the waste lithium ion batteries are also a difficult problem due to the presence of a large amount of substances harmful to the environment.
To solve this problem, researchers are studying a new generation of zinc ion batteries to replace the conventional lithium ion batteries. The zinc ion battery has the following advantages: firstly, the zinc ion battery adopts aqueous electrolyte, and is safe and environment-friendly. Secondly, the reserve of zinc is very abundant, and the preparation technology is simpler compared with a lithium battery, and is beneficial to further reducing the cost of the battery. Thirdly, the zinc ion battery has higher theoretical specific capacity (829mA · h/g) and high power density, which means that the application potential of the zinc ion battery is very huge.
However, rapid capacity fade of zinc ion batteries during cycling has been a challenge to researchers. During charging and discharging processes of the zinc ion battery, a large amount of zinc dendrites are generated on the surface of an electrode, and the zinc dendrites are root causes of capacity attenuation and low cycle life of the zinc ion battery, and even possibly cause short circuit and thorough damage of the battery. This greatly limits the development and application of zinc ion batteries. Therefore, developing a viable solution that can inhibit zinc dendrite growth is key to constructing high performance zinc ion batteries.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides the electrolyte for protecting the electrode of the zinc ion battery and the zinc ion battery, and effectively solves the problems of low cycle life, fast capacity attenuation and the like of the existing zinc ion.
The invention is realized by the following technical scheme:
an electrolyte for protecting a zinc ion battery electrode comprises soluble zinc salt, silicon nanoparticles and deionized water, wherein the concentration of the soluble zinc salt is 0.1-10 mol/L, and the concentration of the silicon nanoparticles is 0.01-10 g/L.
Preferably, the soluble zinc salt is one or more of zinc sulfate, zinc chloride, zinc nitrate, zinc acetate, zinc fluoride, zinc hexafluoro-silicate and zinc trifluoromethanesulfonate.
A zinc ion battery comprises a positive electrode, a negative electrode, a battery diaphragm and the electrolyte for protecting the electrode of the zinc ion battery.
Preferably, the positive electrode is composed of an active material, a conductive agent and a binder; the negative electrode is made of zinc sheets, zinc powder, electrogalvanizing, foamed zinc or a zinc simple substance material; the battery diaphragm is a glass fiber diaphragm.
Preferably, the active material of the positive electrode is a manganese-based material, a vanadium-based material, or a prussian blue-based compound.
The invention has the following beneficial effects:
(1) according to the invention, silicon nanoparticles are introduced into the electrolyte, and the growth of zinc dendrites is realized in the circulation process, so that the electrode of the zinc ion battery is protected, and the circulation life of the zinc ion battery is obviously prolonged.
(2) The electrolyte disclosed by the invention is simple in preparation formula and simple in preparation process operation, and the electrical cycle life and the cycle stability of the zinc ion battery prepared by using the electrolyte are effectively improved through electrochemical tests.
Drawings
FIG. 1 shows a zinc symmetrical cell assembled with a blank electrolyte at 10mA/cm2Current density of 1mA · h/cm2Surface electron microscopy images of zinc electrodes after 10 weeks of cycling at fixed capacity of (a);
FIG. 2 shows a zinc symmetric cell assembled at 10mA/cm using an electrolyte solution with silicon nanoparticles added2Current density of 1mA · h/cm2Surface electron microscopy images of zinc electrodes after 10 weeks of cycling at fixed capacity of (a);
FIG. 3 shows the assembly of a zinc symmetrical cell at 10mA/cm using a common electrolyte2Current density of 1mA · h/cm2Cycle 75h at fixed capacity;
FIG. 4 shows the assembly of a zinc symmetric cell at 10mA/cm using an electrolyte solution with silicon nanoparticles added2Current density of 1mA · h/cm2At a fixed capacity for a cycle time of more than 200 hours-a voltage profile.
Detailed Description
The invention is described in further detail below with reference to specific embodiments and with reference to the following drawings.
Example 1
The electrolyte for protecting the electrode of the zinc-ion battery consists of soluble zinc salt, silicon nanoparticles and deionized water, wherein the soluble zinc salt adopts zinc sulfate (ZnSO)4) Wherein zinc sulfate (ZnSO)4) The concentration of (A) is 1-3 mol/L, the concentration of silicon nanoparticles is 0.1-1 g/L, and the balance is water.
The soluble zinc salt can be one or more of zinc sulfate, zinc chloride, zinc nitrate, zinc acetate, zinc fluoride, zinc hexafluoro-silicate and zinc trifluoromethanesulfonate.
2mg of silicon nanoparticles with 2.87g of ZnSO4Dissolved in 10mL of water and stirred for 24 hours to obtain the target electrolyte.
A zinc ion battery comprises a positive electrode, a negative electrode, electrolyte and a battery diaphragm, wherein the electrolyte is target electrolyte; the positive electrode consists of an active substance, a conductive agent and a binder, wherein the active substance is a manganese-based material, a vanadium-based material or a prussian blue compound; the negative electrode is made of zinc sheets, zinc powder, electrogalvanizing, foamed zinc or a zinc simple substance material; the battery diaphragm is a glass fiber diaphragm.
Test example 1
2.87g of ZnSO4Dissolved in 10mL of water and stirred for 24h to obtain a blank electrolyte.
The target electrolyte and the blank electrolyte prepared in example 1 were used to prepare a zinc symmetrical battery.
The electrochemical test of the zinc ion symmetric battery of the test example is carried out on a LAND-CT2001A battery test system, and the test temperature is kept constant at 25 ℃. The test results were as follows:
(1) comparison of dendrite growth
FIG. 1 shows that the zinc symmetrical battery assembled by using a blank electrolyte is at 10mA/cm2Current density of 1mA · h/cm2The dendritic growth condition of the surface of the zinc electrode after 10 weeks of circulation under the fixed capacity。
FIG. 2 shows that the zinc symmetrical cell assembled by using the target electrolyte is at 10mA/cm2Current density of 1mA · h/cm2The dendritic growth on the surface of the zinc electrode after 10 weeks of cycling at the fixed capacity of (2).
It can be clearly observed that a large number of dendrites are formed on the surface of the zinc electrode when the blank electrolyte is used, while the surface of the zinc electrode is very smooth without dendrite generation when the target electrolyte is used.
(2) Battery cycle life comparison
FIG. 3 shows that the blank electrolyte is used for assembling the zinc symmetrical battery at 10mA/cm2Current density of 1mA · h/cm2Cycle at a fixed capacity of 75 h.
FIG. 4 shows the assembly of a symmetrical zinc cell at 10mA/cm using the target electrolyte2Current density of 1mA · h/cm2Cycling over a time-voltage curve of 200h at a fixed capacity.
As can be seen, in the case of using the blank electrolyte, the zinc symmetrical cell was short-circuited after 67h of cycling. And in the case of using the target electrolyte, the zinc symmetrical battery can stably cycle for more than 210 h. This shows that the cycle life of the zinc symmetric battery is significantly improved after the electrolyte is modified by the silicon nanoparticles.
The foregoing embodiments illustrate the principles, principal features and advantages of the invention, and it will be understood by those skilled in the art that the invention is not limited to the foregoing embodiments, which are merely illustrative of the principles of the invention, and that various changes and modifications may be made therein without departing from the scope of the principles of the invention.
Claims (5)
1. The electrolyte for protecting the electrode of the zinc-ion battery is characterized by comprising soluble zinc salt, silicon nanoparticles and deionized water, wherein the concentration of the soluble zinc salt is 0.1-10 mol/L, and the concentration of the silicon nanoparticles is 0.01-10 g/L.
2. The electrolyte of claim 1, wherein the soluble zinc salt is one or more of zinc sulfate, zinc chloride, zinc nitrate, zinc acetate, zinc fluoride, zinc hexafluoroate, and zinc trifluoromethanesulfonate.
3. A zinc-ion battery comprising a positive electrode, a negative electrode, a battery separator, and the electrolyte according to claim 1 or 2 for protecting an electrode of the zinc-ion battery.
4. The zinc-ion battery of claim 3, wherein the positive electrode comprises an active material, a conductive agent, and a binder; the negative electrode is made of zinc sheets, zinc powder, electrogalvanizing, foamed zinc or a zinc simple substance material; the battery diaphragm is a glass fiber diaphragm.
5. The zinc-ion battery according to claim 4, wherein the active material of the positive electrode is a manganese-based material, a vanadium-based material, or a Prussian blue-based compound.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011109262.3A CN112242571B (en) | 2020-10-16 | 2020-10-16 | Electrolyte for protecting zinc ion battery electrode and zinc ion battery |
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| CN202011109262.3A CN112242571B (en) | 2020-10-16 | 2020-10-16 | Electrolyte for protecting zinc ion battery electrode and zinc ion battery |
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| CN112242571A true CN112242571A (en) | 2021-01-19 |
| CN112242571B CN112242571B (en) | 2022-03-11 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112652825A (en) * | 2021-01-20 | 2021-04-13 | 山东大学 | Low-cost aqueous zinc ion battery electrolyte and preparation method and application thereof |
| CN112919534A (en) * | 2021-01-29 | 2021-06-08 | 山东大学 | Zinc ion battery electrolyte modifier and preparation method and application thereof |
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| CN112919534A (en) * | 2021-01-29 | 2021-06-08 | 山东大学 | Zinc ion battery electrolyte modifier and preparation method and application thereof |
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| CN112242571B (en) | 2022-03-11 |
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Effective date of registration: 20231221 Address after: 461000, 3rd Floor, Office Building, No. 66 Xuzhou Road, Urban Rural Integration Demonstration Zone, Xuchang City, Henan Province Patentee after: Henan Yifan Battery Co.,Ltd. Address before: 221116 No. 101, Shanghai Road, Copper Mt. New District, Jiangsu, Xuzhou Patentee before: Jiangsu Normal University |