CN113161630A - Aqueous secondary battery and aqueous electrolyte - Google Patents
Aqueous secondary battery and aqueous electrolyte Download PDFInfo
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- CN113161630A CN113161630A CN202110569160.8A CN202110569160A CN113161630A CN 113161630 A CN113161630 A CN 113161630A CN 202110569160 A CN202110569160 A CN 202110569160A CN 113161630 A CN113161630 A CN 113161630A
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- 239000003792 electrolyte Substances 0.000 title claims abstract description 57
- 229910001451 bismuth ion Inorganic materials 0.000 claims abstract description 22
- 229910001430 chromium ion Inorganic materials 0.000 claims abstract description 19
- 229910001432 tin ion Inorganic materials 0.000 claims abstract description 19
- 229910001456 vanadium ion Inorganic materials 0.000 claims abstract description 19
- 239000000654 additive Substances 0.000 claims abstract description 18
- 230000000996 additive effect Effects 0.000 claims abstract description 18
- 239000003014 ion exchange membrane Substances 0.000 claims abstract description 18
- -1 hydrogen ions Chemical class 0.000 claims abstract description 16
- 229910001437 manganese ion Inorganic materials 0.000 claims abstract description 16
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 14
- 239000001257 hydrogen Substances 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 39
- 150000001450 anions Chemical class 0.000 claims description 13
- 239000003115 supporting electrolyte Substances 0.000 claims description 10
- 239000008151 electrolyte solution Substances 0.000 claims description 4
- 239000007774 positive electrode material Substances 0.000 claims description 4
- 229910001414 potassium ion Inorganic materials 0.000 claims description 4
- 229910001415 sodium ion Inorganic materials 0.000 claims description 4
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 claims description 3
- 229910001429 cobalt ion Inorganic materials 0.000 claims description 3
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 claims description 3
- 239000007773 negative electrode material Substances 0.000 claims description 3
- 229910001453 nickel ion Inorganic materials 0.000 claims description 3
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 claims description 3
- YPJKMVATUPSWOH-UHFFFAOYSA-N nitrooxidanyl Chemical compound [O][N+]([O-])=O YPJKMVATUPSWOH-UHFFFAOYSA-N 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 27
- 238000006243 chemical reaction Methods 0.000 description 20
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 16
- 229910052799 carbon Inorganic materials 0.000 description 15
- 239000011651 chromium Substances 0.000 description 12
- 238000007600 charging Methods 0.000 description 11
- 238000007599 discharging Methods 0.000 description 10
- 238000000034 method Methods 0.000 description 10
- 239000007788 liquid Substances 0.000 description 9
- 230000008569 process Effects 0.000 description 8
- 239000013543 active substance Substances 0.000 description 7
- 239000003011 anion exchange membrane Substances 0.000 description 7
- 230000009467 reduction Effects 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 239000011149 active material Substances 0.000 description 5
- JHXKRIRFYBPWGE-UHFFFAOYSA-K bismuth chloride Chemical compound Cl[Bi](Cl)Cl JHXKRIRFYBPWGE-UHFFFAOYSA-K 0.000 description 5
- 238000002484 cyclic voltammetry Methods 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 description 4
- 238000003411 electrode reaction Methods 0.000 description 4
- 238000004146 energy storage Methods 0.000 description 4
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 4
- 239000011572 manganese Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000004020 conductor Substances 0.000 description 3
- 238000010277 constant-current charging Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 229910021389 graphene Inorganic materials 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 230000007246 mechanism Effects 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 description 2
- 239000002041 carbon nanotube Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000012983 electrochemical energy storage Methods 0.000 description 2
- 238000006056 electrooxidation reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 230000001965 increasing effect Effects 0.000 description 2
- GEYXPJBPASPPLI-UHFFFAOYSA-N manganese(iii) oxide Chemical compound O=[Mn]O[Mn]=O GEYXPJBPASPPLI-UHFFFAOYSA-N 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 description 1
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 239000012080 ambient air Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000002238 carbon nanotube film Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000005341 cation exchange Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000012612 commercial material Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000004069 differentiation Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 1
- 150000008040 ionic compounds Chemical class 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 150000002696 manganese Chemical class 0.000 description 1
- 229910000357 manganese(II) sulfate Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052987 metal hydride Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 229920000128 polypyrrole Polymers 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 229910052720 vanadium Inorganic materials 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
- H01M2300/00—Electrolytes
- H01M2300/0002—Aqueous electrolytes
- H01M2300/0005—Acid electrolytes
-
- 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
- H01M2300/0011—Sulfuric acid-based
-
- 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
The invention discloses an aqueous secondary battery and an aqueous electrolyte, wherein the aqueous secondary battery comprises: an electrolyte, comprising: manganese ions, hydrogen ions; one of chromium ions, vanadium ions and tin ions; and a bismuth ion additive; a positive current collector; a negative current collector; an ion exchange membrane.
Description
Technical Field
The invention relates to the technical field of novel electrochemical energy storage, in particular to a water-system secondary battery and a water-system electrolyte.
Background
With the excessive consumption of petroleum and non-renewable energy sources and the environmental pollution caused by the excessive consumption, the rational development and utilization of renewable energy sources such as solar energy and wind energy become more and more important. However, these renewable energy sources are limited by geographical and environmental factors due to their severe randomness and intermittency. Therefore, it is important to deploy efficient and convenient energy storage technology. Electrochemical energy storage is considered to be one of the most available energy storage technologies for large-scale applications because it has theoretically excellent advantages, including high round-trip efficiency, long service life, low maintenance cost, high efficiency, no operational pollution, etc. However, the prior art represented by batteries still has various limitations despite rapid development. Taking a lithium ion battery as an example, although the lithium ion battery occupies the mainstream market, the flammable, volatile and toxic organic electrolyte is used, so that continuous safety accidents occur in recent years, and people are always reminded that the safety is an important condition for considering the battery.
Aqueous batteries are a safe alternative to organic batteries, especially for large scale energy storage. First, water has natural characteristics of non-flammability and non-toxicity, which brings about high safety and environmental friendliness to the water-based battery. Secondly, water is considered as a general solvent, can dissolve various ionic compounds, and due to its high dielectric constant and low viscosity, the water-based electrolyte has high ionic conductivity, which also provides a solid foundation for fast charging, high rate and high power density. Third, water-based cells can be assembled in ambient air without creating oxygen-free conditions, thereby greatly reducing manufacturing costs and difficulty. Finally, aqueous batteries reported to date exhibit better cycle life (> 1000 cycles), which is further enhanced compared to organic systems. Therefore, development of a novel water-based battery for large-scale energy storage has practical application prospects in combination with the advantages of the water-based battery.
Disclosure of Invention
Technical problem to be solved
In view of the above problems, the present invention provides a water-based secondary battery, which is used to at least partially solve the technical problems of low energy density, poor rate capability, short cycle life, etc. of the conventional water-based secondary battery.
(II) technical scheme
In order to solve the technical problems, the technical scheme of the invention is as follows:
as one aspect of the present invention, there is provided an aqueous secondary battery including:
an electrolyte, comprising: manganese ions, hydrogen ions; one of chromium ions, vanadium ions and tin ions; and a bismuth ion additive;
a positive current collector;
a negative current collector;
an ion exchange membrane.
In one embodiment, the electrolyte further comprises a supporting electrolyte, wherein the supporting electrolyte comprises one or more of potassium ions, sodium ions, cobalt ions and nickel ions;
wherein the concentration of the supporting electrolyte is 0.0001-10 mol/L.
In one embodiment, the concentration of the chromium ions ranges from 0.01mol/L to 10 mol/L;
the concentration range of the vanadium ions is 0.01-10 mol/L;
the concentration range of the tin ions is 0.01-10 mol/L.
In one embodiment, the concentration range of the manganese ions is 0.01-10 mol/L;
the concentration range of the hydrogen ions is 10 < -6 > to 10 mol/L;
the concentration range of the bismuth ion additive is 0.0001-10 mol/L.
In one embodiment, the concentration of the bismuth ion additive is in the range of 0.005-0.5 mol/L.
In one embodiment, the electrolyte further comprises anions;
wherein the concentration range of the anions is 0.01 mol/L-12 mol/L.
In one embodiment, the anion comprises one or more of sulfate, nitrate, perchlorate, acetate, and carbonate.
In one embodiment, the positive electrode current collector is free of positive electrode active material;
the negative electrode current collector does not contain a negative electrode active material.
In one embodiment, the water-based secondary battery has an operating voltage range of 0 to 4V.
As another aspect of the present invention, there is provided an aqueous electrolyte solution for use in the above-described aqueous secondary battery, comprising: manganese ions, hydrogen ions; one of chromium ions, vanadium ions and tin ions; and a bismuth ion additive.
(III) advantageous effects
1. The invention provides an aqueous secondary battery comprising a divalent manganese ion (Mn) and one of a chromium ion, a vanadium ion and a tin ion2+) Ions, and hydrogen ions (H)+) As an electrolyte, to provide an active material, and divalent manganese ions (Mn) in the solution during charging2+) Electrochemical oxidation reaction occurs on the positive current collector, electrons are lost, and the anode current collector is oxidized into MnO2，MnO2The lost electrons flow to the negative electrode through an external circuit, and one of chromium ions, vanadium ions and tin ions of the negative electrode undergoes valence conversion and surrounds the negative electrode.
Therefore, in the water-based secondary battery provided by the invention, the cathode reaction adopts a deposition and dissolution mechanism of solid-liquid conversion, and the cathode adopts a liquid-liquid reaction with rapid reaction kinetics, so that the water-based secondary battery is not subjected to diffusion control and phase conversion control of ions in an electrode crystal structure, and has ultrahigh power characteristic and overlong cycle life. In addition, the electrolyte of the invention is added with bismuth ion additive, Bi3+The electrode is deposited and dissolved on the surface of the electrode in the charging and discharging processes, and the rate capability of the electrode reaction is obviously promoted.
2. The safe water system electrolyte is adopted, so that the safety performance is greatly improved.
Drawings
FIG. 1 shows an aqueous MnO in an example of the present invention2A reaction mechanism diagram of a Cr/V/Sn secondary battery;
FIG. 2 shows that the electrolyte contains no bismuth ion additive and 0.005mol/L BiCl in the example of the invention3Water system MnO of2-cyclic voltammetry profile of Cr secondary battery;
FIG. 3 shows that the electrolyte contains no bismuth ion additive and 0.1mol/L BiCl in the example of the invention3Water system MnO of2-a charge-discharge diagram of a Cr secondary battery;
FIG. 4 shows that the electrolyte contained 0.1mol/L BiCl in the example of the present invention3Water system MnO of2-different rate discharge profiles of Cr secondary batteries;
FIG. 5 shows that the electrolyte contained 0.5mol/L BiCl in the example of the present invention3Water system MnO of2-a graph of the cycling performance of a Cr secondary battery;
FIG. 6 shows that the electrolyte contained 0.2mol/L BiCl in the example of the present invention3Water system MnO of2-cyclic voltammogram of a V secondary cell;
FIG. 7 shows that the electrolyte contained 0.1mol/L BiCl in the example of the present invention3Water system MnO of2Charging of-Sn Secondary batteriesDischarge profile.
Detailed Description
In order that the objects, technical solutions and advantages of the present invention will become more apparent, the present invention will be further described in detail with reference to the accompanying drawings in conjunction with the following specific embodiments.
According to an embodiment of the present invention, there is provided an aqueous secondary battery including:
an electrolyte, comprising: manganese ions, hydrogen ions; one of chromium ions, vanadium ions and tin ions; and a bismuth ion additive;
a positive current collector;
a negative current collector;
an ion exchange membrane.
The invention provides an aqueous secondary battery comprising one of chromium ions, vanadium ions and tin ions, and divalent manganese ions (Mn)2+) Ions, and hydrogen ions (H)+) As an electrolyte, to provide an active material, and divalent manganese ions (Mn) in the solution during charging2+) Electrochemical oxidation reaction occurs on the positive current collector, electrons are lost, and the anode current collector is oxidized into MnO2，MnO2The lost electrons flow to the negative electrode through an external circuit, and one of chromium ions, vanadium ions and tin ions of the negative electrode undergoes valence conversion and surrounds the negative electrode.
The discharge process of the cell is the reverse of the charge process, as shown in detail in fig. 1, and the main electrode reactions of the cell are summarized as follows:
and (3) charging process:
and (3) positive electrode: mn2++2H2O→MnO2+4H++2e-
Negative electrode: mx++ye-→Mx-y+
And (3) discharging:
and (3) positive electrode: MnO2+4H++2e-→Mn2++2H2O
Negative electrode: mx-y+→Mx++ye-
Wherein M is one of chromium ion, vanadium ion and tin ion.
As described above, during charge-discharge cycles, each charge cycle produces a deposit of positive electrode active material (i.e., solid MnO)2) On the current collector, the cathode has one of high valence state chromium ion, vanadium ion and tin ion converted into low valence state, and the anode is dissolved in electrolyte and the cathode is converted into high valence state ion from low valence state.
Therefore, in the water-based secondary battery provided by the invention, the positive electrode reaction adopts a deposition and dissolution mechanism of solid-liquid conversion, the negative electrode adopts a liquid-liquid reaction with rapid reaction kinetics, and the water-based secondary battery is not subjected to diffusion control and phase conversion control of ions in an electrode crystal structure, and shows ultrahigh power characteristics and overlong cycle life. In addition, the electrolyte of the invention is added with bismuth ion additive, Bi3+The electrode is deposited and dissolved on the surface of the electrode in the charging and discharging processes, and the rate capability of the electrode reaction is obviously promoted.
In addition, the aqueous secondary battery of the present invention employs a safe aqueous electrolyte, so that the safety performance is greatly improved.
According to the embodiment of the invention, the concentration range of manganese ions is 0.01-10 mol/L;
the concentration range of hydrogen ions is 10-6～10mol/L；
The concentration range of the bismuth ion additive is 0.0001-10 mol/L;
one of chromium ions, vanadium ions and tin ions, the concentration range of which is 0.01-10 mol/L.
According to the embodiment of the invention, the concentration range of the bismuth ion additive can be selected to be 0.005-0.5 mol/L.
The concentration of one of chromium ions, vanadium ions and tin ions, the concentration of manganese ions and the concentration of hydrogen ions are in such a wide range, which shows the wide applicability of the water-based secondary battery system, namely, the water-based secondary battery system has good electrochemical performance from high active material content to low active material content.
According to the embodiment of the invention, the electrolyte solution may further include a supporting electrolyte, wherein the supporting electrolyte may be selected from one or more of potassium ions, sodium ions, cobalt ions and nickel ions; and the concentration of the supporting electrolyte is 0.0001-10 mol/L.
The supporting electrolyte has wide functions, and can be used for increasing the ionic conductivity of the electrolyte, namely potassium ion (K)+) Sodium ion (Na)+) And the like have good ionic conductivity, which is beneficial to reducing the polarization of the battery and enhancing the rate capability.
According to the embodiment of the invention, the electrolyte further comprises anions, and the anions can be one or more of sulfate radical, nitrate radical, perchlorate radical, acetate radical and carbonate radical; and the concentration range of the anion is 0.01mol/L to 12 mol/L.
The soluble substances added into the electrolyte can be divalent metal manganese salt, metal salt and acid ionized to generate hydrogen ions; therefore, the anion may be one kind of different anions or a mixture of several different anions, and the anion plays a role of balancing charge neutrality in the electrolyte and is not an active substance.
According to an embodiment of the present invention, the electrolyte of the aqueous secondary battery may be selected as a one-liquid system; the ion exchange membrane can be selected from anion exchange membrane, cation exchange membrane, etc.
In the invention, because the negative electrode relates to liquid-liquid reaction, the designed electrolytic liquid is a single-liquid system, but an ion exchange membrane is required to be used for separation so as to prevent shuttle effect and realize high coulomb efficiency.
According to an embodiment of the present invention, the positive electrode current collector does not contain a positive electrode active material; the negative electrode current collector does not contain a negative electrode active material.
According to the reaction process of the battery, the electrode active substances can be regenerated after each charge-discharge cycle of the battery, namely all the active substances of the battery are in the electrolyte, so that the positive electrode current collector does not contain the positive electrode active substances, the negative electrode current collector does not contain the negative electrode active substances, commercial materials without the active substances can be directly used as the positive electrode current collector and the negative electrode current collector of the battery, extra electrode preparation work is not needed, extra electrode material preparation processes are omitted, the battery manufacturing process is simplified, and the battery production time is saved.
According to an embodiment of the present invention, the current collector (positive current collector or negative current collector) includes various conductive materials, such as carbon materials, including one or a composite of several of carbon felt, carbon paper, carbon cloth, graphite felt, graphene film, graphene net, carbon nanotube film, carbon nanotube paper, conductive activated carbon film, mesoporous carbon film, conductive graphite plate, and conductive graphite net.
On the basis of the above embodiment, the current collector (positive current collector or negative current collector) is modified by a conductive material, where the conductive material includes one or a combination of several materials selected from graphene, mesoporous carbon, carbon nanotubes, activated carbon, polyaniline, polypyrrole, poly (3, 4-ethylenedioxythiophene), manganese dioxide, trimanganese tetroxide, dimanganese trioxide, and manganese oxide; so as to increase the contact area between the electrode and the electrolyte.
According to an embodiment of the present invention, the water-based secondary battery may further include a circulation pump to flow the electrolyte.
In the present invention, the electrolyte can be stored in a stationary state in the battery because the influence of concentration polarization caused by consumption of one of chromium ions, vanadium ions and tin ions and divalent manganese ions during charging can be ignored, and in addition, it is feasible to flow the electrolyte by means of a circulation pump.
According to the embodiment of the present invention, the operating voltage range of the aqueous secondary battery is 0 to 4V.
MnO of positive electrode2/Mn2+The theoretical redox potential of (1.23V), the theoretical potential of one of the negative chromium, vanadium and tin ions to convert is: chromium, vanadium and tin are respectively-0.41V, -0.26V and-0.16V, so after the anode and the cathode are matched, the theoretical discharge potential of the battery is 1.64V, 1.49V and 1.39V, but the theoretical discharge potential of the anode reaction is influenced by the acid concentration, the hydrogen ion concentration rises, and the potential rises, so that the upper limit of the working voltage interval of the battery is 4V; the battery can be completely discharged to reach 100% of the discharge depth because the active materials are in the electrolyte, so that the battery can be directly discharged to 0V.
According to the practice of the inventionFor example, although the coulombic efficiency of the aqueous secondary battery is 90 to 100%, and is always close to 100%, the coulombic efficiency slightly decreases after the surface capacity increases. The coulombic efficiency of the battery is caused by the reversibility of the reaction height of the positive electrode and the negative electrode, MnO2/Mn2+And the coulombic efficiency of two reactions of mutual conversion of metal valence states is always over 95 percent, so that the single-liquid battery with active substances in electrolyte is designed. Therefore, the full battery has higher coulombic efficiency all the time.
As another aspect of the present invention, there is provided an aqueous electrolyte solution for use in the above-described aqueous secondary battery, comprising: manganese ions, hydrogen ions; one of chromium ions, vanadium ions and tin ions; and a bismuth ion additive.
The invention is further illustrated by the following specific examples:
according to an embodiment of the present invention, there is provided an aqueous secondary battery including:
an electrolyte comprising 1mol/L MnCl2、1mol/L CrCl2、0.5mol/L H2SO4And 0.005mol/L BiCl3；
A positive current collector adopts carbon felt;
a negative current collector adopts carbon felt;
an ion exchange membrane, which is an anion exchange membrane;
water system MnO is assembled by the electrolyte, the positive current collector, the negative current collector and the ion exchange membrane2-Cr secondary battery and tested using cyclic voltammetry, the results of which are shown by the solid line in figure 2.
The dotted line in FIG. 2 indicates that the electrolyte of this example does not contain 0.005mol/L BiCl3Cyclic voltammetry test curve.
As can be seen from a comparison of the solid line and the broken line in FIG. 2, when bismuth ions were not contained in the electrolyte, the reduction peak current of the battery was 10mA cm-2The reduction peak potential was only about 1.2V, which is much different from the theoretical value of about 1.6V. When the electrolyte contains bismuth ions, the battery begins to generate a reduction peak at about 1.6V, which is consistent with a theoretical value, and the reduction peak currentEven at approximately 40mA cm-2And in the process, the reduction peak potential still exceeds 1.4V, which shows that the performance of the full battery is improved after the bismuth ion additive is added into the electrolyte.
According to an embodiment of the present invention, there is provided an aqueous secondary battery including:
an electrolyte comprising 2mol/L MnCl2、2mol/L CrCl2、1mol/L H2SO4And 0.01mol/L BiCl3；
A positive current collector adopts carbon felt;
a negative current collector adopts carbon felt;
an ion exchange membrane, which is an anion exchange membrane;
water system MnO is assembled by the electrolyte, the positive current collector, the negative current collector and the ion exchange membrane2-Cr secondary battery and was tested using galvanostatic charging and discharging, the results of which are shown by the solid line in figure 3.
The dotted line in FIG. 3 indicates that the electrolyte of this example does not contain 0.1mol/L BiCl3Constant current charge and discharge curve diagram.
Comparing the solid line with the dotted line in FIG. 3, when bismuth ions were not contained in the electrolyte, the current density was 50mA cm-2In the process, the charging potential is stabilized to be close to 2V, the discharging platform is only about 1.2V, and the overpotential is higher and reaches 800 mV. Adding 0.1mol/L BiCl into the electrolyte3At a current density of 50mA cm-2In the process, the charging potential is stabilized to be close to 1.8V, the discharging platform is as high as about 1.5V, the overpotential is only 300mV, and compared with the time without bismuth ions, the discharging platform of the full battery is increased, the overpotential is reduced, the improvement is very obvious, and the practical application value is improved.
According to an embodiment of the present invention, there is provided an aqueous secondary battery including:
an electrolyte comprising 2mol/L MnCl2，2mol/L CrCl2，1mol/L H2SO4，0.1mol/LBiCl3；
A positive current collector adopts carbon felt;
a negative current collector adopts carbon felt;
an ion exchange membrane, which is an anion exchange membrane;
water system MnO is assembled by the electrolyte, the positive current collector, the negative current collector and the ion exchange membrane2-Cr secondary battery, and carrying out multiplying power test by constant current charging and discharging method, the test result is shown in figure 4.
As can be seen from FIG. 4, the discharge plateau of the battery was good at different magnifications (40C, 220C, 400C, respectively), and was 20mA/cm2The voltage platform reaches 1.57V under the condition of discharge current density, the coulombic efficiency is close to 100 percent, and the voltage platform is obviously improved compared with the discharge platform of commercial nickel-metal hydride batteries with the voltage of about 1.2V. At 200mA/cm2Under the condition of discharge current density, the coulombic efficiency is still close to 100%, the voltage platform is still above 1V, and the excellent rate performance is shown. The current density is 200mA/cm2The multiplying power is as high as 400C, and compared with the traditional organic system lithium ion battery, the multiplying power of 400C is a sudden increase. In addition, a high-rate aqueous battery means high power density, and can partially satisfy the market differentiation demand.
According to an embodiment of the present invention, there is provided an aqueous secondary battery including:
an electrolyte comprising 2mol/L MnCl2，2mol/L CrCl2，1mol/L H2SO4，0.5mol/L BiCl3；
A positive current collector adopts carbon felt;
a negative current collector adopts carbon felt;
an ion exchange membrane, which is an anion exchange membrane;
water system MnO is assembled by the electrolyte, the positive current collector, the negative current collector and the ion exchange membrane2-Cr secondary battery, and adopting constant current charging and discharging method to carry out long cycle stability test, the test result is shown in figure 5.
As can be seen from FIG. 5, the water system MnO2After 12000 cycles, the coulombic efficiency of the-Cr secondary battery is still close to 100%, and excellent cycle stability is exhibited. Compared with the conventional water system lead-acid battery, the cycle time is 500-1000 timesThe ring life, namely the cycle life of 12000 times in the invention, is greatly improved, and has high practical application value.
According to an embodiment of the present invention, there is provided an aqueous secondary battery including:
electrolyte containing 1mol/L VOSO4，1mol/L MnCl2，1mol/L H2SO4And 0.2mol/L BiCl3；
A positive current collector adopts carbon felt;
a negative current collector adopts carbon felt;
an ion exchange membrane, which is an anion exchange membrane;
water system MnO is assembled by the electrolyte, the positive current collector, the negative current collector and the ion exchange membrane2And (3) a Sn secondary battery, and performing a test by adopting a cyclic voltammetry, wherein the test is shown in FIG. 6, and as can be seen from FIG. 6, the reduction peak potential of the battery is 1.2V and is consistent with a theoretical value.
According to an embodiment of the present invention, there is provided an aqueous secondary battery including:
electrolyte comprising 1mol/L SnSO4，1mol/L MnSO4And 1mol/L H2SO4And 0.1mol/L BiCl3；
A positive current collector adopts carbon felt;
a negative current collector adopts carbon felt;
an ion exchange membrane, which is an anion exchange membrane;
water system MnO is assembled by the electrolyte, the positive current collector, the negative current collector and the ion exchange membrane2Secondary batteries of-V and tested by constant current charging and discharging, as shown in figure 7. As can be seen from FIG. 7, the aqueous MnO2The discharge platform of the-V secondary battery is more than 1.5V, the performance of the full battery is improved, and the-V secondary battery has very good application value.
The above-mentioned embodiments are intended to illustrate the objects, technical solutions and advantages of the present invention in further detail, and it should be understood that the above-mentioned embodiments are only exemplary embodiments of the present invention and are not intended to limit the present invention, and any modifications, equivalents, improvements and the like made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. An aqueous secondary battery comprising:
an electrolyte, comprising: manganese ions, hydrogen ions; one of chromium ions, vanadium ions and tin ions; and a bismuth ion additive;
a positive current collector;
a negative current collector;
an ion exchange membrane.
2. The water-based secondary battery according to claim 1,
the electrolyte also comprises a supporting electrolyte, wherein the supporting electrolyte comprises one or more of potassium ions, sodium ions, cobalt ions and nickel ions;
wherein the concentration of the supporting electrolyte is 0.0001-10 mol/L.
3. The water-based secondary battery according to claim 1,
the concentration range of the chromium ions is 0.01-10 mol/L;
the concentration range of the vanadium ions is 0.01-10 mol/L;
the concentration range of the tin ions is 0.01-10 mol/L.
4. The water-based secondary battery according to claim 1,
the concentration range of the manganese ions is 0.01-10 mol/L;
the concentration range of the hydrogen ions is 10-6～10mol/L；
The concentration range of the bismuth ion additive is 0.0001-10 mol/L.
5. The aqueous secondary battery according to claim 4, characterized in that,
the concentration range of the bismuth ion additive is 0.005-0.5 mol/L.
6. The water-based secondary battery according to claim 1,
the electrolyte also comprises anions;
wherein the concentration range of the anions is 0.01 mol/L-12 mol/L.
7. The water-based secondary battery according to claim 6,
the anion comprises one or more of sulfate radical, nitrate radical, perchlorate radical, acetate radical and carbonate radical.
8. The water-based secondary battery according to claim 1,
the positive current collector does not contain a positive active material;
the negative electrode current collector does not contain a negative electrode active material.
9. The water-based secondary battery according to claim 1,
the operating voltage range of the aqueous secondary battery is 0-4V.
10. An aqueous electrolyte solution for use in the aqueous secondary battery according to any one of claims 1 to 9, comprising: manganese ions, hydrogen ions; one of chromium ions, vanadium ions and tin ions; and a bismuth ion additive.
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Application publication date: 20210723 |