CN1627554A - Electrolyte of zinc-bromine battery as non-cyclic electrolyte - Google Patents
Electrolyte of zinc-bromine battery as non-cyclic electrolyte Download PDFInfo
- Publication number
- CN1627554A CN1627554A CNA2003101173531A CN200310117353A CN1627554A CN 1627554 A CN1627554 A CN 1627554A CN A2003101173531 A CNA2003101173531 A CN A2003101173531A CN 200310117353 A CN200310117353 A CN 200310117353A CN 1627554 A CN1627554 A CN 1627554A
- Authority
- CN
- China
- Prior art keywords
- mol
- battery
- electrolyte
- zinc
- bromine
- 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.)
- Pending
Links
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
- Hybrid Cells (AREA)
Abstract
Base on reaction of electrode occurred on positive and negative electrodes, electrolytes in use for positive and negative electrodes are prepared in pertinence. Based on characteristics of charging and discharging batteries, different supplemental electrolyte from liquids for positive and negative electrodes of batteries in sequence operation is studied. The disclosed electrolytes restrain noncyclic self-discharge, dendritic growth and improve capability of batteries.
Description
Technical Field
The invention relates to an electrolyte of a non-circulating electrolyte zinc-bromine battery, which comprises a positive electrolyte and a negative electrolyte of the battery and a battery supplementary electrolyte.
Background
Since the 20 th century, the use of a large number of automobiles causes increasingly serious urban air pollution, and the promotion of the method has to consider that electric automobiles replace fuel automobiles so as to solve the problems of urban environmental pollution and upcoming exhaustion of petroleum resources. With the attention of people on environmental protection and the progress of science and technology, the electric vehicle is bound to become the mainstream vehicle in the 21 st century. The heart of the electric automobile is a power battery, and the power battery of the electric automobile is mainly discharged continuously by medium current or discharged by large current (used for starting, accelerating and climbing) unlike a general automobile starting storage battery. In recent years, the manufacturing technology of power batteries for electric vehicles has been rapidly developed, and in particular, zinc-bromine batteries have the advantages of low cost, long service life, high energy density, good electrical property, capability of working at normal temperature, no pollution, good safety and the like, and are meeting the requirements of power batteries for electric vehicles in many aspects, so that the zinc-bromine batteries are more and more emphasized.
The zinc-bromine battery is mainly divided into two structures, one is a non-circulating electrolyte battery, electrolyte is driven by a circulating pump to continuously circulate in a battery cavity and a liquid storage tank, but because the circulation of the electrolyte inevitably generates uneven liquid flow to generate unbalanced tension on the inner cavity of the battery, the structure of the battery is damaged, the service life of the battery is reduced, and the battery is large in size, complex in structure and high in cost; the other is a non-circulating electrolyte zinc-bromine battery, the electrolyte does not need to flow circularly, the structure is simple, the costis reduced, and the service life of the battery can be obviously prolonged.
The non-circulating zinc-bromine battery is a secondary battery which takes zinc bromide water solution as electrolyte and takes bromine corrosion resistant metal or carbon material as an electrode plate. The non-cyclic zinc-bromine battery has the following negative pole reaction during charging: and (3) positive pole reaction: bromine generated on the positive plate and bromine complexThe mixture binds to form a bromine complex, which precipitates on the surface of the positive electrode.
The self-discharge problem of Zn-Br cells is mainly due to Br produced in the cathode region during charging2With Br in solution-Can react to produce Br3 -With Br5 --Thus increasing the dissolution of bromine. These ions, by diffusion into the anodic region, react directly with the Zn layer on the anode, causing the dissolution of zinc and self-discharge:
therefore, taking various measures to prevent the diffusion of bromine to the anode region is the fundamental approach to solve the problem.
In addition, the Zn-Br battery also has a problem of dendrite growth, in which Zn is deposited on the negative electrode when the Zn-Br battery is charged, and when the zinc reaches a certain thickness, a spongy Zn layer and dendrites appear. The Zn-Br battery has high energy density, if the dendritic growth is not controlled, particularly during deep charging, the dendritic Zn penetrates through a diaphragm to cause short circuit, and the generated hydrogen has corrosion effect on a polar plate of a negative electrode.
Some complexing agents are added into the electrolyte, so that the problem of performance reduction of the battery caused by self-discharge and dendritic crystal growth can be solved. As information on additives for electrolytes, mention may be made of those disclosed in GB-A-1569397, WO-A-9518468. WO-A-9518468 discloses the preparation of A zinc halide battery, wherein all asymmetrically substituted quaternary ammonium salts are mentioned, such as N-ethyl-N-methylmorpholine bromide, N-ethyl-N-methylpyrroline bromide, N-methoxymethyl-N-methylpiperidinium bromate, N-chloromethyl-N-methylpyrrolidium bromate, and the like, using bromine complexing agents; GB-a-1569397 discloses a battery in which the electrolyte contains a single bromine complexing agent: a water-soluble tetra-organically substituted quaternary ammonium salt.
Disclosure of Invention
The invention prepares the electrolyte for the positive and negative electrodes in a targeted way according to the electrode reaction of the positive and negative electrodes of the zinc-bromine battery. According to the characteristics of battery charging and discharging, the electrolyte for subsequent supplement of the battery is also researched, and is different from the battery liquid of the positive electrode and the negative electrode. Thereby inhibiting the self-discharge and dendritic crystal growth of the zinc-bromine battery with non-circulating electrolyte and improving the performance of the battery.
The positive electrode electrolyte is prepared by adding several bromine complexing agents into the electrolyte according to a reaction represented by a formula ② carried out by a positive electrode, wherein the main purpose is to complex bromine generated by the reaction, so that the bromine does not directly react with a negative electrode through a diaphragm to form self-discharge, the added various substances are one or more selected from dodecyl trimethyl ammonium bromide, hexadecyl trimethyl ammonium bromide, tetrabutyl ammonium bromide, triethanolamine, octadecyl trimethyl ammonium bromide, didecyl dimethyl ammonium bromide, N-methyl morpholine or a mixture thereof, bromides of the quaternary ammonium salts can be replaced by corresponding chlorides, the additives are added into a zinc bromide aqueous solution with the concentration of 5mol/L, and the adding amount is 0.001-1.5 mol/L of dodecyl trimethyl ammonium bromide, 0.005-1.3 mol/L of hexadecyl trimethyl ammonium bromide, 0-0.9 mol/L of tetrabutyl ammonium bromide, 0-0.6 mol/L of triethanolamine, 0.01-1.0 mol/L of octadecyl trimethyl ammonium bromide, 0.3mol/L of didecyl dimethyl ammonium bromide, 0.7-0.0.5 mol/L of octadecyl trimethyl ammonium bromide, and the optimal adding amount is 0.0.0-0.5 mol/L of octadecyl trimethyl ammonium bromide, 0.0.0-0.05 mol/L of octadecyl trimethyl ammonium bromide, 0.0.0-0.5 mol/L of octadecyl trimethyl ammonium bromide, and the most optimal amount is 0.0.0.0.0-0.0.0.7 mol/L of octadecyl dimethyl ammonium bromide.
Preparing a negative electrode electrolyte: in the process of charging and discharging of the zinc-bromine battery, the zinc forms dendrite at the edge of the battery to cause short circuit of the battery, and the generated hydrogen has corrosion effect on a polar plate of a negative electrode. The addition of ammonium ions can prevent the generation of zinc dendrites, TX-10 is a corrosion inhibitor of a zinc electrode and can inhibit the precipitation of hydrogen, and chloride ions play a role of a conductivity improver in a solution. The added various substances are potassium chloride, stannic chloride, cadmium chloride, TX-10 and OP-10. The addition amount is potassium chloride: 0-1.5mol/L, stannic chloride: 0-0.2 mol/L, cadmium chloride: 0-0.2 mol/L, TX-10: 0 to 0.2mol/L, OP-10: 0 to 0.2 mol/L. The optimal addition amount is potassium chloride: 0.2-0.5 mol/L, stannic chloride: 0.02-0.14 mol/L, cadmium chloride: 0.01-0.07 mol/L, TX-10: 0.01-0.1 mol/L, OP-10: 0.01 to 0.1 mol/L. In addition to the above additives, the main component of the negative electrolyte is a 5mol/L aqueous solution of zinc bromide.
Electrolyte is added in the using process: since water is largely lost during the charge and discharge of the battery, the molar concentration of the replenishment electrolyte is lower than that of the positive and negative electrode electrolytes. Adding potassium chloride and sodium chloride into 5mol/L zinc bromide electrolyte according to the molar ratio of 1: 1, then diluting with 2-5 times of distilled water, mixing uniformly, and adding into a battery according to the required amount. The chloride ions act as conductivity modifiers in the solution.
The invention can improve the complexing ability of bromine, so free bromine in the electrolyte can be reduced, and the self-discharge phenomenon caused by the existence of the free bromine is reduced. The addition of the solution conductivity improver, the hydrogen inhibiting material and the corrosion inhibitor can improve the conductivity of the battery, reduce the hydrogen gas evolution and prolong the service life of the battery.
Detailed Description
The following examples are intended to illustrate certain preferred embodiments of the invention and are not intended to limit the scope of the invention.
Example 1
Preparing a positive electrolyte: to a 5mol/L aqueous solution of zinc bromide, added are: dodecyl trimethyl ammonium bromide 0.3mol/L, hexadecyl trimethyl ammonium bromide 0.15mol/L, and tetrabutyl ammonium bromide 0.4 mol/L.
Preparing a negative electrode electrolyte: to a 5mol/L aqueous solution of zinc bromide, added are: potassium chloride: 0.5mol/L, stannic chloride: 0.1mol/L, cadmium chloride: 0-0.1 mol/L, TX-10: 0 to 0.01mol/L, OP-10: 0 to 0.01 mol/L.
Specific energy of the battery: 36Wh/Kg, cycle life: more than 600 times
Example 2
Preparing a positive electrolyte: to a 5mol/L aqueous solution of zinc bromide, added are: 0.3mol/L of dodecyl trimethyl ammonium bromide, 0.15mol/L of hexadecyl trimethyl ammonium bromide, 0.4mol/L of tetrabutyl ammonium bromide, 0.1mol/L of triethanolamine, 0.1mol/L of octadecyl trimethyl ammonium bromide, 0.05mol/L of didecyl dimethyl ammonium bromide and 0.1mol/L of N-methylmorpholine.
Preparing a negative electrode electrolyte: to a 5mol/L aqueous solution of zinc bromide, added are: potassium chloride: 0.5mol/L, stannic chloride: 0.1mol/L, cadmium chloride: 0-0.1 mol/L, TX-10: 0 to 0.01mol/L, OP-10: 0 to 0.01 mol/L. Specific energy of the battery: 38Wh/Kg, cycle life: more than 800 times, and the self-discharge rate of the battery at 20 ℃ is less than 18%/day.
Claims (7)
1. An acyclic electrolyte zinc-bromine battery, characterized in that: the battery positive electrolyte contains a plurality of additives capable of forming a complex with the reaction product bromine, including: 0.001-1.5 mol/L of dodecyl trimethyl ammonium bromide, 0.005-1.3 mol/L of hexadecyl trimethyl ammonium bromide, 0-0.9 mol/L of tetrabutyl ammonium bromide, 0-0.6 mol/L of triethanolamine, 0.01-1.0 mol/L of octadecyl trimethyl ammonium bromide, 0-1.3 mol/L of didecyl dimethyl ammonium bromide and 0-0.7 mol/L of N-methylmorpholine.
2. The non-circulating electrolyte zinc-bromine battery of claim 1 wherein: the battery positive electrolyte contains a plurality of additives capable of forming a complex with the reaction product bromine, including: 0.1-0.5 mol/L of dodecyl trimethyl ammonium bromide, 0.05-0.6 mol/L of hexadecyl trimethyl ammonium bromide, 0.01-0.3 mol/L of tetrabutyl ammonium bromide, 0-0.4 mol/L of triethanolamine, 0-0.5 mol/L of octadecyl trimethyl ammonium bromide, 0-0.6 mol/L of didecyl dimethyl ammonium bromide, and 0-0.4 mol/L of N-methylmorpholine.
3. The non-circulating electrolyte zinc-bromine battery of any of claims 1-2 characterized in that: all bromine salts in the additive may be replaced by their corresponding chlorine salts.
4. An acyclic electrolyte zinc-bromine battery, characterized in that: the cathode electrolyte contains a corrosion inhibitor capable of inhibiting hydrogen evolution reaction, wherein: potassium chloride: 0-1.5 mol/L, stannic chloride: 0-0.2 mol/L, cadmium chloride: 0-0.2 mol/L, TX-10: 0 to 0.2mol/L, OP-10: 0 to 0.2 mol/L.
4. The non-circulating electrolyte zinc-bromine battery of claim 4 wherein: the negative electrode electrolyte contains a corrosion inhibitor capable of inhibiting hydrogen evolution reaction, wherein the negative electrode electrolyte comprises: potassium chloride: 0.2-0.5 mol/L, stannic chloride: 0.02-0.14 mol/L, cadmium chloride: 0.01-0.07 mol/L, TX-10: 0.01-0.1 mol/L, OP-10: 0.01 to 0.1 mol/L.
6. The non-circulating electrolyte zinc-bromine battery of any of claims 1, 2, 4 wherein additional battery make-upelectrolyte is added during use of the battery: adding potassium chloride and sodium chloride into 5mol/L zinc bromide electrolyte according to the molar ratio of 1: 1, then diluting with 2-5 times of distilled water, mixing uniformly, and adding into a battery according to the required amount.
7. The non-circulating electrolyte zinc-bromine battery of claim 3 wherein additional battery make-up electrolyte is added during use of the battery: adding potassium chloride and sodium chloride into 5mol/L zinc bromide electrolyte according to the molar ratio of 1: 1, then diluting with 2-5 times of distilled water, mixing uniformly, and adding into a battery according to the required amount.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2003101173531A CN1627554A (en) | 2003-12-11 | 2003-12-11 | Electrolyte of zinc-bromine battery as non-cyclic electrolyte |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2003101173531A CN1627554A (en) | 2003-12-11 | 2003-12-11 | Electrolyte of zinc-bromine battery as non-cyclic electrolyte |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1627554A true CN1627554A (en) | 2005-06-15 |
Family
ID=34760984
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2003101173531A Pending CN1627554A (en) | 2003-12-11 | 2003-12-11 | Electrolyte of zinc-bromine battery as non-cyclic electrolyte |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1627554A (en) |
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102244285A (en) * | 2011-05-24 | 2011-11-16 | 周成壁 | High-concentration zinc-vanadium redox battery |
| CN102479968A (en) * | 2010-11-29 | 2012-05-30 | 中国科学院大连化学物理研究所 | Zinc / polyhalide energy storage cell |
| CN103326055A (en) * | 2012-11-01 | 2013-09-25 | 周谨平 | Zinc cathode electrolyte applied to redox battery |
| CN104051819A (en) * | 2013-03-13 | 2014-09-17 | 沈阳鑫科能源技术有限公司 | Electrolyte additive of electrolyte circulating type zinc air battery |
| CN104752754A (en) * | 2013-12-26 | 2015-07-01 | 苏州宝时得电动工具有限公司 | Electrolyte solution and battery |
| WO2017070340A1 (en) * | 2015-10-21 | 2017-04-27 | Research Foundation Of The City University Of New York | Additive for increasing lifespan of rechargeable zinc-anode batteries |
| JP2019511097A (en) * | 2014-10-06 | 2019-04-18 | エオス エナジー ストレージ， エルエルシー | Electrolyte for rechargeable electrochemical cell |
| CN110767927A (en) * | 2019-10-28 | 2020-02-07 | 武汉工程大学 | Electrolyte for static zinc-bromine liquid battery |
| WO2020076985A1 (en) * | 2018-10-10 | 2020-04-16 | Oregon State University | Aqueous zinc-metal batteries comprising "water-in-salt" electrolyte |
| CN111446508A (en) * | 2020-05-01 | 2020-07-24 | 浙江大学 | High-concentration solution and application and preparation method thereof |
| CN111653788A (en) * | 2020-07-14 | 2020-09-11 | 无锡永华电池有限公司 | Alkaline battery negative electrode material |
| CN111755748A (en) * | 2019-03-29 | 2020-10-09 | 株式会社村田制作所 | Electrolyte additive, electrolyte and lithium ion secondary battery comprising same |
| US10892524B2 (en) | 2016-03-29 | 2021-01-12 | Eos Energy Storage, Llc | Electrolyte for rechargeable electrochemical cell |
| US11424484B2 (en) | 2019-01-24 | 2022-08-23 | Octet Scientific, Inc. | Zinc battery electrolyte additive |
-
2003
- 2003-12-11 CN CNA2003101173531A patent/CN1627554A/en active Pending
Cited By (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102479968A (en) * | 2010-11-29 | 2012-05-30 | 中国科学院大连化学物理研究所 | Zinc / polyhalide energy storage cell |
| CN102244285A (en) * | 2011-05-24 | 2011-11-16 | 周成壁 | High-concentration zinc-vanadium redox battery |
| CN102244285B (en) * | 2011-05-24 | 2016-03-02 | 周成壁 | High-concentration zinc-vanadium redox battery |
| CN103326055A (en) * | 2012-11-01 | 2013-09-25 | 周谨平 | Zinc cathode electrolyte applied to redox battery |
| CN103326055B (en) * | 2012-11-01 | 2016-11-16 | 周谨平 | Zinc cathode electrolyte applied to redox battery |
| CN104051819A (en) * | 2013-03-13 | 2014-09-17 | 沈阳鑫科能源技术有限公司 | Electrolyte additive of electrolyte circulating type zinc air battery |
| CN104051819B (en) * | 2013-03-13 | 2017-02-08 | 沈阳鑫科能源技术有限公司 | Electrolyte additive of electrolyte circulating type zinc air battery |
| CN104752754A (en) * | 2013-12-26 | 2015-07-01 | 苏州宝时得电动工具有限公司 | Electrolyte solution and battery |
| JP2019511097A (en) * | 2014-10-06 | 2019-04-18 | エオス エナジー ストレージ， エルエルシー | Electrolyte for rechargeable electrochemical cell |
| US10276872B2 (en) | 2014-10-06 | 2019-04-30 | Eos Energy Storage, Llc | Electrolyte for rechargeable electrochemical cell |
| US20180316064A1 (en) * | 2015-10-21 | 2018-11-01 | Research Foundation Of The City University Of New New York | Additive for Increasing Lifespan of Rechargeable Zinc-Anode Batteries |
| WO2017070340A1 (en) * | 2015-10-21 | 2017-04-27 | Research Foundation Of The City University Of New York | Additive for increasing lifespan of rechargeable zinc-anode batteries |
| US10910674B2 (en) | 2015-10-21 | 2021-02-02 | Research Foundation Of The City University Of New New York | Additive for increasing lifespan of rechargeable zinc-anode batteries |
| US10892524B2 (en) | 2016-03-29 | 2021-01-12 | Eos Energy Storage, Llc | Electrolyte for rechargeable electrochemical cell |
| US11942606B2 (en) | 2016-03-29 | 2024-03-26 | EOS Energy Technology Holdings, LLC | Electrolyte for rechargeable electrochemical cell |
| WO2020076985A1 (en) * | 2018-10-10 | 2020-04-16 | Oregon State University | Aqueous zinc-metal batteries comprising "water-in-salt" electrolyte |
| US11424484B2 (en) | 2019-01-24 | 2022-08-23 | Octet Scientific, Inc. | Zinc battery electrolyte additive |
| CN111755748A (en) * | 2019-03-29 | 2020-10-09 | 株式会社村田制作所 | Electrolyte additive, electrolyte and lithium ion secondary battery comprising same |
| CN110767927A (en) * | 2019-10-28 | 2020-02-07 | 武汉工程大学 | Electrolyte for static zinc-bromine liquid battery |
| CN111446508A (en) * | 2020-05-01 | 2020-07-24 | 浙江大学 | High-concentration solution and application and preparation method thereof |
| CN111653788A (en) * | 2020-07-14 | 2020-09-11 | 无锡永华电池有限公司 | Alkaline battery negative electrode material |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111211360B (en) | Additive modified aqueous zinc ion colloidal electrolyte and preparation method thereof | |
| CN1627554A (en) | Electrolyte of zinc-bromine battery as non-cyclic electrolyte | |
| CN109509901B (en) | Alkaline zinc-iron flow battery | |
| JPS62216176A (en) | Electrolyte for redox battery | |
| CN110190332A (en) | Nickelic tertiary cathode material system battery electrolytic solution and lithium ion battery | |
| CN114039109B (en) | Additive for aqueous zinc ion battery electrolyte, aqueous zinc ion battery electrolyte and aqueous zinc ion battery | |
| CN108711633A (en) | Electrolyte for zinc-bromine flow battery | |
| CN110767927A (en) | Electrolyte for static zinc-bromine liquid battery | |
| CN108832164A (en) | A kind of lead fluid cell electrolyte containing compound additive | |
| CN108470949B (en) | A kind of lead-acid accumulator is with high-efficiency activated dose and preparation method thereof | |
| CN114388901A (en) | Aqueous zinc ion battery electrolyte and battery | |
| CN114039108A (en) | High-temperature-resistant aqueous zinc ion battery electrolyte and preparation method and application thereof | |
| CN112635860A (en) | Aqueous zinc ion battery electrolyte additive | |
| CN113437340A (en) | Positive electrode electrolyte for zinc-manganese flow battery | |
| CN115863799A (en) | Electrolyte additive for zinc battery and application thereof | |
| CN114725537A (en) | Water-based zinc ion battery electrolyte capable of inhibiting zinc dendrite and side reaction and application thereof | |
| CN114388859B (en) | Negative electrode electrolyte for all-iron flow battery | |
| CN1791945A (en) | Zinc lanthanide sulfonic acid electrolytes | |
| Bogomolov et al. | Alkaline Ni− Zn Rechargeable Batteries for Sustainable Energy Storage: Battery Components, Deterioration Mechanisms, and Impact of Additives | |
| CN113823840A (en) | Electrolyte for lithium metal cathode | |
| CN111416139A (en) | Electrolyte corrosion inhibitor, aluminum-air battery, alkaline electrolyte and preparation method thereof | |
| CN105119018A (en) | Electrolyte of lithium ion battery and lithium ion battery | |
| CN114551954B (en) | Negative electrode electrolyte for zinc-iron flow battery | |
| CN114094208A (en) | Electrolyte for aqueous zinc ion battery and aqueous zinc ion battery | |
| CN117594884A (en) | Water-based zinc ion battery electrolyte and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |