CN116247312A - Water system sodium ion battery - Google Patents

Water system sodium ion battery Download PDF

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Publication number
CN116247312A
CN116247312A CN202310160623.4A CN202310160623A CN116247312A CN 116247312 A CN116247312 A CN 116247312A CN 202310160623 A CN202310160623 A CN 202310160623A CN 116247312 A CN116247312 A CN 116247312A
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Prior art keywords
electrolyte
ion battery
sodium ion
additive
current collector
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丁波
李明珠
熊明文
武聪聪
李明刚
丁南南
汤冬洁
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Suzhou Nazhu New Energy Technology Co ltd
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Suzhou Nazhu New Energy Technology Co ltd
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    • 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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/669—Steels
    • 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
    • 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

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Secondary Cells (AREA)
  • Cell Electrode Carriers And Collectors (AREA)

Abstract

The invention discloses a water system sodium ion battery, and belongs to the technical field of water system batteries. The water-based sodium ion battery comprises an anode current collector and electrolyte, wherein the anode current collector comprises a rolled high alloy metal foil; the electrolyte is added with an additive combined by a corrosion inhibitor and a surfactant, wherein the mass of the additive accounts for 1-10% of the total mass of the electrolyte. The positive current collector is stainless steel foil, has stronger corrosion resistance and higher strength, and is beneficial to the capacity exertion of the battery and the cycle performance of the battery by being matched with the added electrolyte additive.

Description

Water system sodium ion battery
Technical Field
The invention belongs to the technical field of water-based batteries, and particularly relates to a water-based sodium ion battery.
Background
With the continuous development of society, the performance requirements of electrochemical energy storage devices are also continuously improved, and particularly, the energy density of batteries and the power performance of the batteries are improved; meanwhile, the battery is safe, green and environment-friendly, and has higher requirements, namely a novel battery: the aqueous ion energy storage battery is applied, and the aqueous ion battery adopts the saline solution as electrolyte, so that the problem of flammability of organic electrolyte is avoided, the defects of high pollution, short service life (such as a lead-acid battery) and high price (a nickel-hydrogen battery) of the traditional aqueous battery are overcome, and the aqueous ion battery has the characteristics of safety, low cost, long service life, environment friendliness, recoverability and the like, is a novel battery, and is also an ideal system for large-scale energy storage technology requirements.
More recently, a water-based zinc ion battery is disclosed, wherein the battery adopts a zinc anode and a zinc cathode, and an additive is added into electrolyte of the battery, wherein the water-based double ion battery disclosed in Chinese patent application No. CN202110564940.3 comprises a cathode, an anode and electrolyte between the cathode and the anode, the additive can be added into the electrolyte, and the additive can form a solid electrolyte membrane on at least one electrode surface of the cathode and the anode; the additive may include urea and/or vinylene carbonate; also, for example, chinese patent application number CN202110663229.3 discloses a water-based zinc ion battery electrolyte containing an additive, and a preparation method and a battery thereof, wherein the electrolyte additive is a lanthanum-containing compound (such as lanthanum sulfate, lanthanum nitrate, lanthanum chloride, lanthanum acetate, and hydrates thereof). The electrolyte additive can form a protective layer on the surface of zinc metal through adsorption or deposition in the zinc metal deposition process; further, chinese patent application number CN202111318079.9 discloses an additive for aqueous zinc ion battery electrolyte, aqueous zinc ion battery electrolyte and aqueous zinc ion battery; the additive for the aqueous zinc ion battery electrolyte is water-soluble chitosan; the mass of the additive accounts for 0.1-10% of the total mass of the electrolyte; further, for example, chinese patent application number CN202210745644.8 discloses an additive for an electrolyte, and application thereof, an electrolyte and a water-based zinc ion battery, wherein the expression of the electrolyte additive is as follows: [ XMIM ] Y, wherein [ XMIM ] is 1-alkyl-3-methylimidazole cation, alkyl is one or a combination of more of ethyl, butyl, hexyl or octyl, and Y is anion; further, chinese patent application number CN202210484551.4 discloses the use of functionalized boron nitride as an electrolyte additive, aqueous electrolyte, zinc ion battery/capacitor; introducing a functionalized boron nitride additive into the electrolyte; further, as disclosed in chinese patent application No. CN202110014019.1, an electrolyte containing lignin and gelatin compound additives and a water-based zinc ion battery using the electrolyte are disclosed, wherein the electrolyte is prepared by uniformly mixing lignin modified substance, gelatin and aqueous electrolyte; another example is chinese patent application No. CN202110903319.5 which discloses a mixed water system ion battery electrolyte comprising sodium salt, zinc salt, manganese salt and organic compound additive; the organic compound additive is one or more of sodium dodecyl sulfate and sodium dodecyl benzene sulfonate; another example is chinese patent application No. CN202110981039.6 which discloses a water-based zinc ion battery electrolyte and a battery, the electrolyte comprises: zinc salt solution, sodium polyalkylsulfonate and salt containing cations in a battery anode material, wherein the alkyl number of the sodium polyalkylsulfonate is 10-30; this patent is made by adding a surfactant, sodium polyalkylsulfonate, as an additive component to the electrolyte.
Most of the disclosed patent additives act on a zinc cathode and rarely act on an anode current collector, but in the assembly and application process of the water-based ion energy storage battery, the anode current collector of the battery is one of core components of an electric core, and plays a role of a mechanical carrier serving as an active particle material and providing an electron migration channel. At present, the working environment of the positive electrode current collector of the water-based ion energy storage battery is bad, and the oxidation in the saline solution electrolyte under a higher working potential is needed to be dealt with, and chemical and electrochemical corrosion is overcome, so that the capacity exertion of a battery system is limited, the long-term working of the battery is not facilitated, and the cycle life of the battery is seriously influenced. In addition, if the positive current collector is improperly selected, the battery will be directly disabled.
Disclosure of Invention
1. Problems to be solved
Aiming at the problem that the positive electrode current collector has corrosion to affect the use, the invention aims to provide a water-based sodium ion battery which is beneficial to the capacity exertion of the battery and the cycle performance of the battery.
2. Technical proposal
In order to achieve the above purpose, the present invention adopts the following technical scheme:
the water-based sodium-ion battery comprises a positive current collector and electrolyte, wherein the positive current collector comprises a rolled high-alloy metal foil; the electrolyte is added with an additive combined by a corrosion inhibitor and a surfactant, wherein the mass of the additive accounts for 1-10% of the total mass of the electrolyte.
In one possible embodiment of the present invention, the rolled high alloy metal foil is a stainless steel foil having a thickness of 10 μm to 50 μm and a yield strength of 800 to 1200MPa.
In one possible embodiment of the present invention, the stainless steel foil includes, but is not limited to: 200 series, 300 series, 400 series, 500 series, 600 series, and one or more of martensite-ferrite, austenite-martensite transition type complex phase stainless steel and precipitation hardening stainless steel having a martensite-carbide structure.
In one possible embodiment of the present invention, the corrosion inhibitor includes, but is not limited to, one or more of chromate, sodium silicate, and disodium hydrogen phosphate; the surfactant includes, but is not limited to, one or more of propenyl thiourea, sodium dodecyl sulfonate, silicone, acetic acid, urea and aniline.
In one possible embodiment of the invention, the mass of the additive is 3-8% of the total mass of the electrolyte.
In one possible embodiment of the present invention, the mass ratio of the corrosion inhibitor to the surfactant in the additive is 1: (1-9).
In one possible embodiment of the present invention, the corrosion inhibitor includes, but is not limited to, one or more of chromate, sodium silicate, and disodium hydrogen phosphate; the surfactant is acetic acid or urea.
In one possible embodiment of the present invention, the corrosion inhibitor is one or more of chromate, sodium silicate and disodium hydrogen phosphate; the surfactant is propenyl thiourea.
In one possible embodiment of the invention, the corrosion inhibitor is chromate; the surfactant is a silicone.
The invention also provides a water-based sodium ion battery with Na 0.44 MnO 2 ‖Na 2 SO 4 +ZnSO 4 The II Zn battery system comprises a positive current collector of a stainless steel foil and an additive formed by adding a corrosion inhibitor and a surfactant into electrolyte to form a water-based sodium ion battery system, wherein the battery circulates for 100 circles under the 1C multiplying power, and the capacity retention rate is more than 90%.
3. Advantageous effects
Compared with the prior art, the invention has the beneficial effects that:
(1) The positive current collector of the water-based sodium-ion battery is stainless steel foil, has stronger corrosion resistance and higher strength, is matched with the added electrolyte additive, is favorable for the capacity exertion of the battery and the cycle performance of the battery, and can be cycled for 100 circles under the 1C multiplying power, and the capacity retention rate is more than 90%;
(2) The stainless steel foil with good acid-base corrosion resistance and high strength is adopted as the positive current collector of the water-based ion battery, so that the corrosion resistance and the tab strength of the positive current collector of the water-based ion battery are enhanced; compared with common aluminum foil and copper foil current collectors, the aluminum foil and copper foil current collector has stronger service life and corrosion resistance, is beneficial to improving the yield of manufacturing and processing of positive pole pieces, is beneficial to confluence welding of metal strips, and is easy to form mass production.
Drawings
The technical solution of the present invention will be described in further detail below with reference to the accompanying drawings and examples, but it should be understood that these drawings are designed for the purpose of illustration only and thus are not limiting the scope of the present invention. Moreover, unless specifically indicated otherwise, the drawings are intended to conceptually illustrate the structural configurations described herein and are not necessarily drawn to scale.
FIG. 1 is a SEM microcosmic profile of a current collector after cycling of inventive example 1 and comparative example 1, comparative example 2;
fig. 2 is a graph showing charge-discharge cycle performance of the battery according to example 1 of the present invention.
Detailed Description
The following detailed description and example embodiments of the invention may be better understood when read in conjunction with the accompanying drawings, in which elements and features of the invention are identified by reference numerals.
The raw materials used in the present invention are not specifically described, and are commercially available, for example, stainless steel foil may be produced using tai steel stainless, and the like.
The water-based sodium-ion battery comprises a positive current collector and electrolyte, wherein the positive current collector comprises a rolled high-alloy metal foil; the electrolyte is added with an additive combined by a corrosion inhibitor and a surfactant, wherein the mass of the additive accounts for 1-10% of the total mass of the electrolyte. The additive of the electrolyte can react with the matrix tissue on the surface of the positive current collector to form an electrolyte membrane, so that the effect of the stainless steel foil positive current collector and the brine electrolyte is slowed down, the surface oxidation and corrosion of the positive current collector are effectively prevented, and the effect of improving the electrical performance of the water-based sodium-ion battery is achieved; in addition, the additive can effectively inhibit the growth of zinc dendrites and effectively solve the problems of zinc corrosion, passivation of zinc cathodes and the like.
Further, the corrosion inhibitor includes, but is not limited to, one or more of chromate, sodium silicate and disodium hydrogen phosphate; the surfactant is acetic acid or urea. Chromates, including but not limited to lithium chromate, sodium chromate, but not copper chromate, can dissolve in the electrolyte as copper ions disrupt the ionization balance in the electrolyte, on the one hand, to replenish the electrolyte in the electrolyte, and on the other hand, chromates change in crystal form structure upon initial discharge and react with the surface of the positive current collector to form a thicker electrolyte membrane.
Further, the corrosion inhibitor is one or more of chromate, sodium silicate and disodium hydrogen phosphate; the surfactant is propenyl thiourea. The propenyl thiourea promotes the ion in the electrolyte to be uniformly adsorbed on the surface of the stainless steel foil, so that the reaction is uniformly carried out on the whole surface, and the electrolyte membrane is fine in crystallization and flat and smooth in surface.
Further, the corrosion inhibitor is chromate; the surface active agent is siloxane ketone, wherein the effective combination of chromate and siloxane ketone can form a layer of electrolyte membrane with higher density on the surface of the positive electrode current collector, and compared with the electrolyte membrane disclosed at present, the electrolyte membrane has the advantage of better preventing the surface oxidation and corrosion of the positive electrode current collector.
Example 1
Aqueous sodium ion Na 0.44 MnO 2 ‖Na 2 SO 4 +ZnSO 4 In a Zn battery system, positive and negative electrode plates are prepared by homogenate coating, a stainless steel foil with the yield strength of 800MPa is selected as a positive electrode current collector, a universal copper foil is selected as a negative electrode current collector, and a combination of sodium chromate, acetic acid and urea is selected as electrolyte additives, wherein the added mass accounts for 1% of chromate, 6% of acetic acid and 3% of urea of the total mass of the electrolyte, and the mixture is added into 1mol/LNa 2 SO 4 +2mol/LZnSO 4 In the electrolyte, the prepared positive and negative electrode plates, the electrolyte and the non-woven fabric diaphragm pass through the positive electrode plate, the diaphragm, the negative electrode plate, the diaphragm, the positive electrode plate, the diaphragm and the negative electrode plate, and Na is assembled in the assembly sequence 0.44 MnO 2 ‖Na 2 SO 4 +ZnSO 4 II Zn water system sodium ion battery cell.
Comparative example 1
This comparative example is substantially the same as example 1 except that an Al foil is used for the positive electrode current collector and no additive is added to the electrolyte.
Comparative example 2
This comparative example is substantially the same as example 1 except that 300 series stainless steel foil is used for the positive electrode current collector, and no additive is added to the electrolyte.
The battery prepared according to example 1 was tested, and the battery was cycled at 1C rate, normally cycled for 100 cycles, with a detected capacity retention of 92.5% of the initial discharge specific capacity, and a better capacity retention, and charge-discharge cycle performance as shown in fig. 2.
The post-corrosion SEM microtomography of the current collector after cycling for example 1, comparative example 1 and comparative example 2 is shown in fig. 1; the positive electrode current collectors of comparative example 1 and comparative example 2 all showed severe corrosion, thereby affecting the normal use of the battery.
Example 2
Aqueous sodium ion Na 0.44 MnO 2 ‖Na 2 SO 4 +ZnSO 4 In a Zn battery system, positive and negative electrode plates are prepared by homogenate coating, a 10 mu m 400-series stainless steel foil with the yield strength of 1000MPa is selected as a positive current collector, a universal copper foil is selected as a negative current collector, lithium chromate and siloxane ketone are selected as electrolyte additives, wherein the added mass is 1% of chromate and 1% of siloxane ketone which account for the total mass of the electrolyte, and the electrolyte additives are added into 1mol/LNa 2 SO 4 +2mol/LZnSO 4 In the electrolyte, the prepared positive and negative electrode plates, the electrolyte and the non-woven fabric diaphragm pass through the positive electrode plate, the diaphragm, the negative electrode plate, the diaphragm, the positive electrode plate, the diaphragm and the negative electrode plate, and Na is assembled in the assembly sequence 0.44 MnO 2 ‖Na 2 SO 4 +ZnSO 4 II Zn water system sodium ion battery cell.
The battery prepared in accordance with example 2 was tested, and cycled at 1C rate for 100 cycles of normal cycle, with a test capacity retention of 91.8% of the initial cycle discharge specific capacity.
Example 3
Aqueous sodium ion Na 0.44 MnO 2 ‖Na 2 SO 4 +ZnSO 4 In a Zn battery system, positive and negative electrode plates are prepared by homogenate coating, a positive electrode current collector adopts a 50 μm austenitic-martensitic transition type complex phase stainless steel foil with yield strength of 1200MPa, a negative electrode current collector adopts a general copper foil, an electrolyte additive adopts a combination of sodium chromate, acetic acid and urea, wherein the added mass accounts for the total weight of the electrolyte1% by mass of chromate, 3% by mass of acetic acid and 4% by mass of urea, is added to 1mol/LNa 2 SO 4 +2mol/LZnSO 4 In the electrolyte, the prepared positive and negative electrode plates, the electrolyte and the non-woven fabric diaphragm pass through the positive electrode plate, the diaphragm, the negative electrode plate, the diaphragm, the positive electrode plate, the diaphragm and the negative electrode plate, and Na is assembled in the assembly sequence 0.44 MnO 2 ‖Na 2 SO 4 +ZnSO 4 II Zn water system sodium ion battery cell.
The battery prepared in accordance with example 3 was tested, and cycled at 1C rate for 100 cycles of normal cycle, with a test capacity retention of 92.1% of the initial cycle discharge specific capacity.
Example 4
Aqueous sodium ion Na 0.44 MnO 2 ‖Na 2 SO 4 +ZnSO 4 In a Zn battery system, positive and negative electrode plates are prepared by homogenate coating, a 30 mu m stainless steel foil with the yield strength of 900MPa is selected as a positive electrode current collector, a universal copper foil is selected as a negative electrode current collector, and a combination of sodium chromate, sodium silicate and propenyl thiourea is selected as electrolyte additives, wherein the added mass accounts for 1% of the total mass of the electrolyte, 3% of sodium silicate and 4% of propenyl thiourea, and the electrolyte additives are added into 1mol/LNa 2 SO 4 +2mol/LZnSO 4 In the electrolyte, the prepared positive and negative electrode plates, the electrolyte and the non-woven fabric diaphragm pass through the positive electrode plate, the diaphragm, the negative electrode plate, the diaphragm, the positive electrode plate, the diaphragm and the negative electrode plate, and the NNa is assembled in the assembly sequence 0.44 MnO 2 ‖Na 2 SO 4 +ZnSO 4 II Zn water system sodium ion battery cell.
The battery prepared in accordance with example 3 was tested, and cycled at 1C rate for 100 cycles of normal cycle, with a test capacity retention of 90.8% of the initial cycle discharge specific capacity.
Example 5
Aqueous sodium ion Na 0.44 MnO 2 ‖Na 2 SO 4 +ZnSO 4 In the II Zn battery system, positive and negative electrode plates are prepared by homogenate coating, and a positive current collector is selected30 μm yield strength is 1000MPa austenite-martensite transition type complex phase stainless steel foil, the negative current collector is general copper foil, the electrolyte additive is chromate, sodium silicate and propenyl thiourea, wherein the added chromate and propenyl thiourea account for 1% of the total mass of the electrolyte, 3% of the total mass of the electrolyte, and the total mass of the electrolyte is added into 1mol/LNa 2 SO 4 +2mol/LZnSO 4 In the electrolyte, the prepared positive and negative electrode plates, the electrolyte and the non-woven fabric diaphragm pass through the positive electrode plate, the diaphragm, the negative electrode plate, the diaphragm, the positive electrode plate, the diaphragm and the negative electrode plate, and Na is assembled in the assembly sequence 0.44 MnO 2 ‖Na 2 SO 4 +ZnSO 4 II Zn water system sodium ion battery cell.
The battery prepared in accordance with example 3 was tested, and cycled at 1C rate for 100 cycles of normal cycle, with a test capacity retention of 92.2% of the initial cycle discharge specific capacity.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential characteristics thereof. The present embodiments are, therefore, to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein. Any reference sign in a claim should not be construed as limiting the claim concerned.

Claims (10)

1. The water-based sodium ion battery comprises a positive electrode current collector and electrolyte, and is characterized in that the positive electrode current collector comprises a rolled high alloy metal foil; the electrolyte is added with an additive combined by a corrosion inhibitor and a surfactant, wherein the mass of the additive accounts for 1-10% of the total mass of the electrolyte.
2. The aqueous sodium ion battery of claim 1, wherein the rolled high alloy metal foil is a stainless steel foil having a thickness of 10 μm to 50 μm and a yield strength of 800 to 1200MPa.
3. The aqueous sodium ion battery of claim 2, wherein the stainless steel foil includes, but is not limited to: 200 series, 300 series, 400 series, 500 series, 600 series, and one or more of martensite-ferrite, austenite-martensite transition type complex phase stainless steel and precipitation hardening stainless steel having a martensite-carbide structure.
4. The aqueous sodium ion battery of claim 3 wherein the corrosion inhibitor includes, but is not limited to, one or more of chromate, sodium silicate and disodium hydrogen phosphate; the surfactant includes, but is not limited to, one or more of propenyl thiourea, sodium dodecyl sulfonate, silicone, acetic acid, urea and aniline.
5. The aqueous sodium ion battery according to claim 1, wherein the mass of the additive is 3 to 8% of the total mass of the electrolyte.
6. The aqueous sodium ion battery according to claim 1, wherein the mass ratio of the corrosion inhibitor to the surfactant in the additive is 1: (1-9).
7. The aqueous sodium ion battery of claim 4 wherein the corrosion inhibitor includes, but is not limited to, one or more of chromate, sodium silicate and disodium hydrogen phosphate; the surfactant is acetic acid or urea.
8. The aqueous sodium ion battery of claim 4 wherein the corrosion inhibitor is one or more of the group consisting of, but not limited to, chromate, sodium silicate and disodium hydrogen phosphate; the surfactant is propenyl thiourea.
9. The aqueous sodium ion battery of claim 4 wherein the corrosion inhibitor is chromate; the surfactant is a silicone.
10. An aqueous sodium ion battery having Na 0.44 MnO 2 ‖Na 2 SO 4 +ZnSO 4 The II Zn battery system comprises a positive current collector of a stainless steel foil and an additive formed by adding a corrosion inhibitor and a surfactant into electrolyte to form a water-based sodium ion battery system, wherein the battery circulates for 100 circles under the 1C multiplying power, and the capacity retention rate is over 92.5 percent.
CN202310160623.4A 2023-02-24 2023-02-24 Water system sodium ion battery Pending CN116247312A (en)

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