[go: up one dir, main page]

CN112751086A - Zinc ion battery - Google Patents

Zinc ion battery Download PDF

Info

Publication number
CN112751086A
CN112751086A CN202011583219.0A CN202011583219A CN112751086A CN 112751086 A CN112751086 A CN 112751086A CN 202011583219 A CN202011583219 A CN 202011583219A CN 112751086 A CN112751086 A CN 112751086A
Authority
CN
China
Prior art keywords
zinc
ion battery
ion
electrolyte
battery
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
Application number
CN202011583219.0A
Other languages
Chinese (zh)
Inventor
罗云峰
刘正军
罗小松
陈璞
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Ruihai Bo Changzhou Energy Technology Co ltd
Original Assignee
Individual
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Individual filed Critical Individual
Priority to CN202011583219.0A priority Critical patent/CN112751086A/en
Publication of CN112751086A publication Critical patent/CN112751086A/en
Pending legal-status Critical Current

Links

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
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0568—Liquid materials characterised by the solutes
    • 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
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • 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
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0569—Liquid materials characterised by the solvents
    • 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
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0025—Organic electrolyte
    • 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
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0025—Organic electrolyte
    • H01M2300/0028—Organic electrolyte characterised by the solvent
    • H01M2300/0037—Mixture of solvents
    • 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

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

本发明公开了一种锌离子电池，其中，所述锌离子电池的电解液包括磷酸酯类溶剂和含锌离子的盐。该锌离子电池通过采用包括磷酸酯类溶剂和含锌离子的盐的有机电解液，可以有效解决现有锌离子电池中正极活性物质易溶出、易析氢/析氧、电压窗口低以及锌负极枝晶生长等问题，从而可以提高锌离子电池的比容量、循环性能和安全性。The invention discloses a zinc ion battery, wherein the electrolyte of the zinc ion battery includes a phosphate ester solvent and a salt containing zinc ions. The zinc ion battery can effectively solve the problem of easy dissolution of positive active materials, easy hydrogen/oxygen evolution, low voltage window and zinc negative electrode branch in the existing zinc ion battery by using an organic electrolyte including a phosphate solvent and a salt containing zinc ions. Therefore, the specific capacity, cycle performance and safety of zinc-ion batteries can be improved.

Description

Zinc ion battery
Technical Field
The invention belongs to the technical field of batteries, and particularly relates to a zinc ion battery.
Background
In a rechargeable battery, an electrolyte is a key component, and its physical and chemical properties have an important influence on the service life, electrochemical properties, and the like of the battery. Manganese-based (e.g. LiMn)2O4、MnO2) Vanadium based (e.g. V)2O5) In the case of a battery having a positive electrode made of a material and a negative electrode made of zinc, an aqueous electrolyte solution, i.e., H, is often used2O is used as a solvent, and a metal salt electrolyte is added. However, the use of the above-mentioned aqueous electrolyte has the following drawbacks: (1) active substance dissolution: when the positive electrode material contacts H2O, there is a dissolution phenomenon of active materials, resulting in a collapse of the structure of the positive electrode material, thereby affecting the capacity and cycle performance of the battery. Especially manganese-based, vanadium-based, etc. materials as positive electrodeVery often, the dissolution phenomenon of active substances is very obvious; (2) gas evolution: the zinc ion battery adopts water-based electrolyte, and has a gassing phenomenon, so that a battery system is unstable; (3) the voltage window is low: the decomposition voltage of water limits the voltage window of the water-based battery not to be too high; (4) the metallic zinc cathode has the problem of zinc dendrite growth in the traditional aqueous electrolyte, which can reduce the safety and cycle life of the zinc ion battery.
Therefore, the existing zinc ion battery is yet to be improved.
Disclosure of Invention
The present invention is directed to solving, at least to some extent, one of the technical problems in the related art. Therefore, an object of the present invention is to provide a zinc ion battery, which can effectively solve the problems of easy dissolution of an active material of a positive electrode, easy hydrogen/oxygen evolution, a low voltage window, dendritic growth of a zinc negative electrode, and the like in the conventional zinc ion battery by using an organic electrolyte comprising a phosphate solvent and a salt containing zinc ions, so as to improve the specific capacity, the cycle performance, and the safety of the zinc ion battery.
In one aspect of the invention, a zinc ion battery is provided. According to an embodiment of the present invention, the electrolyte of the zinc ion battery includes a phosphate-based solvent and a salt containing zinc ions.
According to the zinc ion battery provided by the embodiment of the invention, the electrolyte comprising the phosphate solvent and the zinc ion salt is adopted, the zinc ion salt can be well dissolved in the phosphate solvent, and the electrolyte does not contain water, so that metal ions generated by the anode material in the discharging process are not dissolved in the electrolyte, thus the dissolution of the anode active substance can be effectively inhibited, the structure of the anode material is stabilized, and the capacity and the cycle performance of the zinc ion battery can be further improved; secondly, the active substance of the anode material is an oxidant, has catalytic performance, is easy to generate catalytic reaction when contacting with the aqueous electrolyte, separates out oxygen, and the cathode zinc is corroded by the aqueous electrolyte and is easy to separate out hydrogen, and the electrolyte can effectively avoid the battery capacity attenuation, swelling and even explosion caused by the gassing side reaction in the electrolyte, and is beneficial to maintaining the stability of a battery system; in addition, the electrolyte has higher decomposition voltage compared with an aqueous electrolyte, the voltage window of the battery is expanded, and the overcharge resistance of the battery is improved; in addition, the electrolyte and the zinc cathode interface have high stability, can guide the uniform deposition of zinc, prevent the formation and growth of dendrites, and improve the safety and the cycle life of the battery. Therefore, the electrolyte can effectively solve the problems of easy dissolution of positive active substances, easy hydrogen/oxygen evolution, low voltage window, dendritic growth of zinc negative electrodes and the like in the conventional zinc ion battery, so that the specific capacity, the cycle performance and the safety of the zinc ion battery can be improved.
In addition, the zinc-ion battery according to the above embodiment of the invention may also have the following additional technical features:
in some embodiments of the present invention, the phosphate-based solvent includes at least one of trimethyl phosphate and triethyl phosphate or a mixture of at least one of trimethyl phosphate and triethyl phosphate and at least one of ethylene glycol, polyethylene glycol, glycerol, dimethyl carbonate, ethylene carbonate, and propylene carbonate. Thus, the salt containing zinc ions can be well dissolved in the phosphate-based solvent.
In some embodiments of the invention, the salt comprising a zinc ion comprises at least one of zinc tetrafluoroborate, zinc perchlorate, zinc methanesulfonate, zinc sulfate, zinc nitrate, zinc oxalate, zinc benzenesulfonate, zinc p-toluenesulfonate, and zinc isooctoate. Thereby, zinc ions can be supplied to the battery.
In some embodiments of the invention, the concentration of zinc ions in the electrolyte is 0.5-5 mol/L. Therefore, the electrochemical performance of the zinc ion battery is better.
In some embodiments of the invention, the salt comprising zinc ions further comprises a second ion, wherein the second ion comprises at least one of a sodium ion, a manganese ion, a potassium ion, a lithium ion, and a magnesium ion. Therefore, the electrochemical performance of the zinc ion battery is better.
In some embodiments of the present invention, the concentration of the second ion in the electrolyte is 0.1-1 mol/L. Therefore, the electrochemical performance of the zinc ion battery is better.
In some embodiments of the invention, the positive electrode of the zinc-ion battery comprises at least one of a manganese-based material and a vanadium-based material.
In some embodiments of the invention, the positive electrode comprises LiMn2O4、MnO2、Mn2O3MnO and V2O5At least one of (a).
In some embodiments of the invention, the negative electrode of the zinc-ion battery comprises at least one of metallic zinc and a zinc-containing compound. Therefore, the metal zinc and the zinc-containing compound have rich sources, low cost, low toxicity, good conductivity, low equilibrium potential and high hydrogen overpotential.
In some embodiments of the invention, the separator of the zinc-ion battery comprises at least one of an AGM glass fiber membrane, a sulfonated separator, a PP membrane and a PE membrane.
Additional aspects and advantages of the invention will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the invention.
Drawings
The above and/or additional aspects and advantages of the present invention will become apparent and readily appreciated from the following description of the embodiments, taken in conjunction with the accompanying drawings of which:
fig. 1 is a capacity fade curve for the zinc ion cells in example 1 and comparative example 1;
fig. 2 is an SEM image of the positive electrode after 20 cycles of the zinc ion battery in example 1(a) and comparative example 1 (b);
fig. 3 is an SEM image of the negative electrode after 20 cycles of the zinc ion battery in example 4(a) and comparative example 2 (b).
Detailed Description
Reference will now be made in detail to embodiments of the present invention, examples of which are illustrated in the accompanying drawings, wherein like or similar reference numerals refer to the same or similar elements or elements having the same or similar function throughout. The embodiments described below with reference to the drawings are illustrative and intended to be illustrative of the invention and are not to be construed as limiting the invention.
In one aspect of the invention, a zinc ion battery is provided. According to an embodiment of the present invention, the electrolyte of the zinc ion battery includes a phosphate-based solvent and a salt containing zinc ions.
The inventor finds that by adopting the electrolyte comprising the phosphate solvent and the zinc ion-containing salt, the zinc ion-containing salt can be well dissolved in the phosphate solvent, and because the electrolyte contains no water, metal ions generated in the discharge process of the positive electrode material are not dissolved in the electrolyte, so that the dissolution of positive electrode active substances can be effectively inhibited, the structure of the positive electrode material is stabilized, and the capacity and the cycle performance of the zinc ion battery can be improved; secondly, the active substance of the anode material is an oxidant, has catalytic performance, is easy to generate catalytic reaction when contacting with the aqueous electrolyte, separates out oxygen, and the cathode zinc is corroded by the aqueous electrolyte and is easy to separate out hydrogen, and the electrolyte can effectively avoid the battery capacity attenuation, bulging and even explosion caused by the gassing side reaction in the electrolyte, thereby being beneficial to the stability of a battery system; in addition, the electrolyte has higher decomposition voltage compared with an aqueous electrolyte, the voltage window of the battery is expanded, and the overcharge resistance of the battery is improved; in addition, the electrolyte and the zinc cathode interface have high stability, can guide the uniform deposition of zinc, prevent the formation and growth of dendrites, and improve the safety and the cycle life of the battery.
It should be noted that, a specific type of the phosphate-based solvent may be selected by those skilled in the art according to actual needs, for example, the phosphate-based solvent includes at least one of trimethyl phosphate and triethyl phosphate or a mixture of at least one of trimethyl phosphate and triethyl phosphate and at least one of ethylene glycol, polyethylene glycol, glycerol, dimethyl carbonate, ethylene carbonate and propylene carbonate. The inventor finds that compared with other organic solvents, trimethyl phosphate and triethyl phosphate have flame retardant performance, the danger of combustion and even explosion is avoided, and the safety is guaranteed, and the addition of ethylene glycol, polyethylene glycol, glycerol dimethyl carbonate, ethylene carbonate and propylene carbonate can improve the ion conduction rate of the phosphate solvents, improve the rate capability of the battery, have an induction effect on the transmission of metal cations, and further improve the stability of the electrolyte and the interface between the positive electrode and the negative electrode. Meanwhile, the specific type of the salt containing zinc ions may be selected by those skilled in the art according to actual needs, for example, the salt containing zinc ions includes at least one of zinc tetrafluoroborate, zinc perchlorate, zinc methanesulfonate, zinc sulfate, zinc nitrate, zinc oxalate, zinc benzenesulfonate, zinc p-toluenesulfonate, and zinc isooctanoate.
Further, the concentration of zinc ions in the electrolyte is 0.5 to 5mol/L, specifically, 0.5mol/L, 1mol/L, 1.5mol/L, 2mol/L, 2.5mol/L, 3mol/L, 3.5mol/L, 4mol/L, 4.5mol/L, or 5 mol/L. The inventor finds that if the concentration of zinc ions in the electrolyte is too low, the battery capacity is not exerted; and if the concentration of zinc ions in the electrolyte is too high, the cycle performance of the battery is not facilitated. Therefore, by adopting the zinc ion concentration, the zinc ion battery has better specific capacity and cycle performance.
In addition, the above salt containing a zinc ion further includes a second ion, wherein the second ion includes at least one of a sodium ion, a manganese ion, a potassium ion, a lithium ion, and a magnesium ion. The inventors have found that the cycle performance and rate performance of the battery are improved by adding the above second ion. The reason is that firstly, the addition of the second ions has a synergistic effect with zinc ions, so that the transmission rate of metal cations is improved; and secondly, a part of second ions are embedded into the anode material, so that the crystal structure of the material is supported, the structural stability of the anode material during ion embedding/extraction is facilitated, and the cycle performance of the battery is improved.
Further, the concentration of the second ions in the electrolyte is 0.1-1 mol/L. The inventor finds that if the concentration of the second ions in the electrolyte is too low, the synergistic effect with zinc ions is not obvious, and the structural support effect on the anode material is not obvious, so that the rate capability and the cycle performance of the battery are not obviously improved; if the concentration of the second ions in the electrolyte is too high, the activity of the zinc ions is affected, and the excessive second ions tend to deposit on the surface of the positive pole piece, so that the embedding/extracting process of the zinc ions is affected. Therefore, the second ions with the concentration can improve the rate performance and the cycle performance of the battery and avoid the influence on the activity of the zinc ions.
It should be noted that, the specific types of the positive electrode, the negative electrode and the separator of the zinc ion battery can be selected by those skilled in the art according to actual needs, for example, the positive electrode includes at least one of a manganese-based material and a vanadium-based material, and specifically, the positive electrode includes LiMn2O4、MnO2、Mn2O3MnO and V2O5At least one of; the negative electrode includes at least one of metallic zinc and a zinc-containing compound; the separator includes at least one of an AGM glass fiber film, a sulfonated separator, a PP film and a PE film.
The inventor finds that by adopting the electrolyte comprising the phosphate solvent and the zinc ion-containing salt, the zinc ion-containing salt can be well dissolved in the phosphate solvent, and because the electrolyte contains no water, metal ions generated in the discharge process of the positive electrode material are not dissolved in the electrolyte, so that the dissolution of positive electrode active substances can be effectively inhibited, the structure of the positive electrode material is stabilized, and the capacity and the cycle performance of the zinc ion battery can be improved; secondly, the active substance of the anode material is an oxidant, has catalytic performance, is easy to generate catalytic reaction when contacting with the aqueous electrolyte, separates out oxygen, and the cathode zinc is corroded by the aqueous electrolyte and is easy to separate out hydrogen, and the electrolyte can effectively avoid the battery capacity attenuation, bulging and even explosion caused by the gassing side reaction in the electrolyte, thereby being beneficial to the stability of a battery system; in addition, the electrolyte has higher decomposition voltage compared with an aqueous electrolyte, the voltage window of the battery is expanded, and the overcharge resistance of the battery is improved; in addition, the electrolyte and the zinc cathode interface have high stability, can guide the uniform deposition of zinc, prevent the formation and growth of dendrites, and improve the safety and the cycle life of the battery. In conclusion, the electrolyte can effectively solve the problems that the active substance of the positive electrode in the existing zinc ion battery is easy to dissolve out, hydrogen/oxygen is easy to separate out, the voltage window is low, the dendritic crystal of the zinc negative electrode grows and the like, so that the specific capacity, the cycle performance and the safety of the zinc ion battery can be improved.
The following embodiments of the present invention are described in detail, and it should be noted that the following embodiments are exemplary only, and are not to be construed as limiting the present invention. In addition, all reagents used in the following examples are commercially available or can be synthesized according to methods herein or known, and are readily available to those skilled in the art for reaction conditions not listed, if not explicitly stated.
Example 1
Assembling the battery: MnO was used in this experiment2The anode is made of zinc foil, the cathode is made of zinc foil, and the diaphragm is an AGM diaphragm. Electrolyte solution: trimethyl phosphate (TMP) as solvent, zinc tetrafluoroborate as zinc salt, Zn dissolved in TMP2+The concentration is 1.2 mol/L;
and (3) testing the battery: in an environment of 25 ℃, the battery is discharged firstly under the current density of 50mA/g and the voltage range of 0.8-1.9V, the initial specific capacity is 215.4mAh/g, the capacity is kept to be 212.6mAh/g after 20 circles, and the capacity retention rate is 98.7% (as shown in figure 1). The battery is amplified to a 5Ah capacity level, and the gas production condition of the battery is detected by adopting a drainage method: no gas was collected. The shape of the anode after 20 cycles is shown in figure 2a, and MnO can be seen2The spherical structure is stable, and the structure collapse does not occur.
Example 2
The procedure of example 1 was repeated except that trimethyl phosphate (TMP) was replaced with triethyl phosphate (TEP).
The electrical properties are shown as: the initial specific capacity is 214.3mAh/g, the capacity is kept to be 211.7mAh/g after 20 circles, and the capacity retention rate is 98.8%.
Example 3
The procedure of example 1 was repeated except that trimethyl phosphate (TMP) was replaced with a mixed solution of trimethyl phosphate and dimethyl carbonate (DMC) (mass ratio TMP: DMC 4: 1).
The electrical properties are shown as: the initial capacity is 217.1mAh/g, the capacity is kept to be 216.2mAh/g after 20 circles, and the capacity retention rate is 99.6%.
Example 4
The procedure is as in example 1 except that zinc tetrafluoroborate is replaced by zinc perchlorate.
The electrical properties are shown as: the initial specific capacity is 210.9mAh/g, the capacity is kept at 208.7mAh/g after 20 circles, and the capacity retention rate is 99.0%. Fig. 3a is an SEM of the cathode after 20 cycles, which shows that the surface of the cathode is still relatively flat after 20 cycles.
Example 5
The anode material is made of MnO2Change to LiMn2O4The test temperature is 45 ℃ high-temperature environment. The rest is the same as example 1.
The electrical properties are shown as: the initial specific capacity is 110.6mAh/g, and the capacity is kept to be 93.2% after 150 circles.
Example 6
The anode material is made of MnO2Is changed to V2O5Otherwise, the same procedure as in example 1 was repeated.
The electrical properties are shown as: the initial specific capacity is 236mAh/g, the capacity is maintained to be 228.7mAh/g after 20 circles, and the capacity retention rate is 96.9%.
Example 7
The electrolyte Zn2+The concentration was changed from 1.2mol/L to 0.6mol/L, and the same was applied to example 1.
The electrical properties are shown as: the initial specific capacity is 209.3mAh/g, the capacity is kept to be 198.2mAh/g after 20 circles, and the capacity retention rate is 94.7%.
Example 8
The electrolyte Zn2+The concentration was changed from 1.2mol/L to 2.5mol/L, and the procedure was otherwise the same as in example 1.
The electrical properties are shown as: the initial specific capacity is 221.0mAh/g, the capacity is kept to be 200.9mAh/g after 20 circles, and the capacity retention rate is 90.9%.
Example 9
The electrolyte further includes sodium ions with a concentration of 0.1mol/L, and the other steps are the same as those of example 1.
The electrical properties are shown as: the initial specific capacity is 215.8mAh/g, the capacity is maintained to be 212.9mAh/g after 20 circles, and the capacity retention rate is 98.7%.
Example 10
The electrolyte further includes manganese ions, the concentration of the manganese ions is 0.3mol/L, and the other steps are the same as those of the embodiment 1.
The electrical properties are shown as: the initial specific capacity is 216.1mAh/g, the capacity is maintained to be 213.0mAh/g after 20 circles, and the capacity retention rate is 98.6%.
Example 11
The electrolyte further contained potassium ions, the concentration of potassium ions was 0.6mol/L, and the other steps were the same as in example 1.
The electrical properties are shown as: the initial specific capacity is 215.6mAh/g, the capacity is kept to be 212.1mAh/g after 20 circles, and the capacity retention rate is 98.4%.
Example 12
The electrolyte solution further included lithium ions, the concentration of which was 0.8mol/L, and the other steps were the same as in example 1.
The electrical properties are shown as: the initial specific capacity is 214.8mAh/g, the capacity is kept to be 211.5mAh/g after 20 circles, and the capacity retention rate is 98.5%.
Example 13
The electrolyte further included magnesium ions at a concentration of 1mol/L, as in example 1.
The electrical properties are shown as: the initial specific capacity is 214.5mAh/g, the capacity is kept to be 211.1mAh/g after 20 circles, and the capacity retention rate is 98.4%.
Comparative example 1
The electrolyte is replaced by a water system electrolyte (Zn) commonly used in the prior art2+1.2mol/L aqueous zinc sulfate solution), otherwise the same as in example 1.
The electrical properties are shown as: the initial specific capacity of the battery under the current density of 50mA/g is 208.8mAh/g, the capacity is kept to be 191.8mAh/g after 20 circles, and the capacity retention rate is 91.9 percent (shown in figure 1).
The battery is amplified to 5Ah capacity level, and the gas production condition of the battery is detected by adopting a drainage method: 0.12mL/Ah/h, and obvious gassing phenomenon exists.
Reason why comparative example 1 is inferior in electrical properties to example 1: first, MnO accompanying the charging and discharging process2Part of Mn in (1)2+Will dissolve in waterIn the process, the structure of the positive active material is collapsed, and the electrical property is influenced; secondly, gassing causes side reactions. MnO in TMP etc. organic electrolyte2Mn in (1)2+Can not be dissolved in the electrolyte, and has stable appearance. The shape of the anode after 20 cycles is shown in figure 2b, and MnO can be seen2The structural collapse was evident.
Comparative example 2
Changing the solvent from TMP to H2O, otherwise the same as example 4.
The electrical properties are shown as: the initial specific capacity is 210.5mAh/g, the capacity is maintained to be 207.2mAh/g after 20 circles, the capacity retention rate is 98.4%, but the dendritic phenomenon of the negative electrode is more prominent, and the negative electrode copper material current collector is corroded. It is predicted that dendrites will puncture the separator after long cycles leading to cell shorting or cell failure due to current collector corrosion. Fig. 3b is an SEM image of the anode after 20 cycles, and it can be seen that there is zinc dendrite stacking on the surface of the anode after 20 cycles.
Comparative example 3
The anode material is made of MnO2Change to LiMn2O4The test temperature is 45 ℃ high-temperature environment. The rest is the same as in comparative example 1. The electrical properties are shown as: the initial specific capacity is 110.3mAh/g, and the capacity is kept to be 83.5 percent after 150 circles.
In the description herein, references to the description of the term "one embodiment," "some embodiments," "an example," "a specific example," or "some examples," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, various embodiments or examples and features of different embodiments or examples described in this specification can be combined and combined by one skilled in the art without contradiction.
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made to the above embodiments by those of ordinary skill in the art within the scope of the present invention.

Claims (10)

1. The zinc ion battery is characterized in that an electrolyte of the zinc ion battery comprises a phosphate solvent and a salt containing zinc ions.
2. The zinc-ion battery of claim 1, wherein the phosphate-based solvent comprises at least one of trimethyl phosphate and triethyl phosphate or a mixture of at least one of trimethyl phosphate and triethyl phosphate with at least one of ethylene glycol, polyethylene glycol, glycerol, dimethyl carbonate, ethylene carbonate, and propylene carbonate.
3. The zinc-ion battery of claim 1, wherein the salt of a zinc-containing ion comprises at least one of zinc tetrafluoroborate, zinc perchlorate, zinc methanesulfonate, zinc sulfate, zinc nitrate, zinc oxalate, zinc benzenesulfonate, zinc p-toluenesulfonate, and zinc isooctanoate.
4. The zinc ion battery according to claim 1 or 3, wherein the concentration of zinc ions in the electrolyte is 0.5 to 5 mol/L.
5. The zinc-ion battery of claim 1, wherein the salt comprising zinc ions further comprises a second ion, wherein the second ion comprises at least one of a sodium ion, a manganese ion, a potassium ion, a lithium ion, and a magnesium ion.
6. The zinc ion battery according to claim 5, wherein the concentration of the second ion in the electrolyte is 0.1 to 1 mol/L.
7. The zinc-ion battery of claim 1, wherein the positive electrode of the zinc-ion battery comprises at least one of a manganese-based material and a vanadium-based material.
8. The zinc-ion battery of claim 7, wherein the positive electrode comprises LiMn2O4、MnO2、Mn2O3MnO and V2O5At least one of (a).
9. The zinc-ion battery of claim 1, wherein the negative electrode of the zinc-ion battery comprises at least one of metallic zinc and a zinc-containing compound.
10. The zinc-ion battery of claim 1, wherein the separator of the zinc-ion battery comprises at least one of an AGM glass fiber membrane, a sulfonated separator, a PP membrane, and a PE membrane.
CN202011583219.0A 2020-12-28 2020-12-28 Zinc ion battery Pending CN112751086A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202011583219.0A CN112751086A (en) 2020-12-28 2020-12-28 Zinc ion battery

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202011583219.0A CN112751086A (en) 2020-12-28 2020-12-28 Zinc ion battery

Publications (1)

Publication Number Publication Date
CN112751086A true CN112751086A (en) 2021-05-04

Family

ID=75646300

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202011583219.0A Pending CN112751086A (en) 2020-12-28 2020-12-28 Zinc ion battery

Country Status (1)

Country Link
CN (1) CN112751086A (en)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113725500A (en) * 2021-09-03 2021-11-30 中南大学 Mixed electrolyte of water-based zinc ion battery
CN114039107A (en) * 2021-10-11 2022-02-11 瑞海泊有限公司 Manganese-zinc secondary battery of oil-water heterogeneous electrolyte system
CN114039108A (en) * 2021-11-10 2022-02-11 湖北大学 A kind of high temperature resistant aqueous zinc ion battery electrolyte and preparation method and application thereof
WO2022233342A1 (en) * 2021-05-06 2022-11-10 陈璞 Aqueous electrolyte and battery
CN115332646A (en) * 2022-08-11 2022-11-11 北京航空航天大学 An electrolyte for high temperature safe water-based zinc ion secondary battery, its preparation method and application
CN116387521A (en) * 2023-03-27 2023-07-04 天津大学 Application of electrocatalyst as self-dehydrogenation catalyst in water system energy storage device
EP4318717A4 (en) * 2022-06-07 2024-07-24 Contemporary Amperex Technology Co., Limited NON-AQUEOUS ELECTROLYTE AND PREPARATION METHOD THEREFOR, AS WELL AS SECONDARY BATTERY AND ELECTRICAL DEVICE COMPRISING SAME

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20160036106A1 (en) * 2013-08-29 2016-02-04 Lg Chem, Ltd. Electrolyte solution for zinc air battery and zinc air battery comprising the same
CN107634266A (en) * 2017-08-18 2018-01-26 上海交通大学 A kind of MH secondary battery flame-retardant electrolyte
CN108242560A (en) * 2017-12-26 2018-07-03 深圳先进技术研究院 Zinc-based double-ion battery and preparation method thereof
CN108574085A (en) * 2018-03-22 2018-09-25 复旦大学 A low-temperature zinc-ion battery
WO2019183224A1 (en) * 2018-03-20 2019-09-26 University Of Maryland, College Park Electrolytes for rechargeable zn-metal battery
CN110994045A (en) * 2019-11-20 2020-04-10 瑞海泊(青岛)能源科技有限公司 Zinc ion battery and method of making the same
CN111509306A (en) * 2020-04-26 2020-08-07 河北大学 Electrolyte for rechargeable zinc ion battery, preparation method of electrolyte and rechargeable zinc ion battery
CN111934033A (en) * 2020-08-20 2020-11-13 江苏师范大学 Method for protecting zinc ion battery electrode

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20160036106A1 (en) * 2013-08-29 2016-02-04 Lg Chem, Ltd. Electrolyte solution for zinc air battery and zinc air battery comprising the same
CN107634266A (en) * 2017-08-18 2018-01-26 上海交通大学 A kind of MH secondary battery flame-retardant electrolyte
CN108242560A (en) * 2017-12-26 2018-07-03 深圳先进技术研究院 Zinc-based double-ion battery and preparation method thereof
WO2019183224A1 (en) * 2018-03-20 2019-09-26 University Of Maryland, College Park Electrolytes for rechargeable zn-metal battery
CN108574085A (en) * 2018-03-22 2018-09-25 复旦大学 A low-temperature zinc-ion battery
CN110994045A (en) * 2019-11-20 2020-04-10 瑞海泊(青岛)能源科技有限公司 Zinc ion battery and method of making the same
CN111509306A (en) * 2020-04-26 2020-08-07 河北大学 Electrolyte for rechargeable zinc ion battery, preparation method of electrolyte and rechargeable zinc ion battery
CN111934033A (en) * 2020-08-20 2020-11-13 江苏师范大学 Method for protecting zinc ion battery electrode

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
陈加航等: "锌金属可充电电池研究现状及展望", 《硅酸盐学报》, vol. 48, no. 7, 31 July 2020 (2020-07-31), pages 1004 - 1012 *

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022233342A1 (en) * 2021-05-06 2022-11-10 陈璞 Aqueous electrolyte and battery
CN113725500A (en) * 2021-09-03 2021-11-30 中南大学 Mixed electrolyte of water-based zinc ion battery
CN114039107A (en) * 2021-10-11 2022-02-11 瑞海泊有限公司 Manganese-zinc secondary battery of oil-water heterogeneous electrolyte system
CN114039108A (en) * 2021-11-10 2022-02-11 湖北大学 A kind of high temperature resistant aqueous zinc ion battery electrolyte and preparation method and application thereof
CN114039108B (en) * 2021-11-10 2024-03-26 湖北大学 High Wen Shuiji-resistant zinc ion battery electrolyte and preparation method and application thereof
EP4318717A4 (en) * 2022-06-07 2024-07-24 Contemporary Amperex Technology Co., Limited NON-AQUEOUS ELECTROLYTE AND PREPARATION METHOD THEREFOR, AS WELL AS SECONDARY BATTERY AND ELECTRICAL DEVICE COMPRISING SAME
CN115332646A (en) * 2022-08-11 2022-11-11 北京航空航天大学 An electrolyte for high temperature safe water-based zinc ion secondary battery, its preparation method and application
CN115332646B (en) * 2022-08-11 2024-05-31 北京航空航天大学 Electrolyte for high-temperature safe water-based zinc ion secondary battery, preparation method and application thereof
CN116387521A (en) * 2023-03-27 2023-07-04 天津大学 Application of electrocatalyst as self-dehydrogenation catalyst in water system energy storage device

Similar Documents

Publication Publication Date Title
CN112751086A (en) Zinc ion battery
JP4629902B2 (en) Method for manufacturing lithium secondary battery
CN110600804B (en) Lithium ion battery electrolyte suitable for NCM811 and SiO-C material system and preparation method thereof
CN103515607B (en) A kind of lithium ion battery cathode slurry, negative pole and battery
CN110556493B (en) Functional composite separator for lithium/sodium secondary battery and preparation method thereof
CN101212048A (en) Anode material of Li-ion secondary battery and battery containing the same
KR20020078660A (en) Separators for winding-type lithium secondary batteries comprising gel-type polymer electrolytes and manufacturing method for the same
CN109256587A (en) Lithium metal secondary battery electrolyte and the lithium metal secondary battery for using the electrolyte
CN102881861A (en) High-temperature lithium ion battery anode slice
CN114039108B (en) High Wen Shuiji-resistant zinc ion battery electrolyte and preparation method and application thereof
CN113948771A (en) Safe low-concentration electrolyte for lithium battery and application thereof
CN110911689A (en) Current collector and preparation method thereof, electrode sheet and secondary battery
CN113690397B (en) A kind of zinc negative pole piece and its preparation method and application
CN109167063A (en) A kind of lithium anode and its preparation method and application of artificial solid electrolyte interface layer protection
US20220271280A1 (en) A lithium negative electrode with protective layer, preparation method and application thereof
CN113299996A (en) Non-aqueous electrolyte for lithium ion battery with ternary positive electrode material and negative electrode silicon-oxygen-carbon composite negative electrode material
WO2022233342A1 (en) Aqueous electrolyte and battery
CN101197436A (en) Positive plate of lithium ion secondary battery, and battery including the same
US20100062327A1 (en) Non-toxic alkaline electrolyte with additives for rechargeable zinc cells
CN108832180A (en) A kind of lithium-ion battery electrolytes and the lithium ion battery comprising the electrolyte
CN109346726A (en) A kind of high temperature modification manganese systems lithium battery anode
CN116288301A (en) A kind of preparation method of air stability protective layer on lithium metal surface
CN115548437A (en) An anion-regulated electrolyte for lithium metal batteries
CN110265720B (en) High-concentration lithium bis (fluorosulfonyl) imide-lithium nitrate-1, 3-dioxolane electrolyte, preparation method thereof and corresponding battery
FI130647B1 (en) Improved rechargeable batteries and production thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
TA01 Transfer of patent application right
TA01 Transfer of patent application right

Effective date of registration: 20230410

Address after: 66 Tianshan Road, Xinbei District, Changzhou City, Jiangsu Province

Applicant after: Ruihai Bo (Changzhou) Energy Technology Co.,Ltd.

Address before: 93 crescent, Waterloo Valley ridge, Ontario

Applicant before: Chen Pu

WD01 Invention patent application deemed withdrawn after publication
WD01 Invention patent application deemed withdrawn after publication

Application publication date: 20210504