CN112490458A - Preparation method of zinc salt mixed electrolyte and manganese positive electrode material for zinc-manganese battery - Google Patents
Preparation method of zinc salt mixed electrolyte and manganese positive electrode material for zinc-manganese battery Download PDFInfo
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- CN112490458A CN112490458A CN202011388559.8A CN202011388559A CN112490458A CN 112490458 A CN112490458 A CN 112490458A CN 202011388559 A CN202011388559 A CN 202011388559A CN 112490458 A CN112490458 A CN 112490458A
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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
- H01M6/00—Primary cells; Manufacture thereof
- H01M6/04—Cells with aqueous electrolyte
- H01M6/045—Cells with aqueous electrolyte characterised by aqueous electrolyte
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- 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
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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
- H01M4/00—Electrodes
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
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- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/621—Binders
- H01M4/622—Binders being polymers
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- H—ELECTRICITY
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- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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- H—ELECTRICITY
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- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
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Abstract
The invention provides a preparation method of a zinc salt mixed electrolyte and a manganese anode material for a zinc-manganese battery 2 The electrolyte is based on zinc salt electrolyte, and certain diluted acid is added to adjust the pH value of the electrolyte. In addition, the positive electrode material contains a certain conductive carbon material, a binder and MnO 2 The conductivity of the battery anode material is improved by ball milling and mixing; the invention adds certain diluted acid into the electrolyte, and then the electrolyte is H + Can promote Mn in the battery in the charging and discharging process 4+ /Mn 2+ The electrochemical performance of the zinc-manganese battery is improved, the battery capacity of the zinc-manganese battery assembled by the material is greatly improved, the discharge platform is improved, and the discharge capacity is obviously improved. The invention has low preparation energy consumption and low raw material price, and can realize industrial production.
Description
Technical Field
The invention relates to the technical field of batteries, in particular to a preparation method of a positive electrode material and a zinc salt electrolyte of a zinc-manganese battery.
Background
China is the biggest world in terms of zinc-manganese battery production and consumption, and the zinc-manganese battery is one of battery families, and has the advantages of simple technology, simple and convenient manufacture, low cost, stability and safety, and long-term occupation of the battery leading position. The zinc-manganese battery is widely applied to daily life of thousands of households.
Benefiting from the advantages of standardization, lightweight, high capacity, low price, safety, stability and the like, so that various small portable electronic appliances, wireless Bluetooth equipment, children toys and the like can seek the use trace of the zinc-manganese battery, and the zinc-manganese battery occupies the market of the field of disposable batteries for a long time and can last for a period of time in the future.
Manganese dioxide (MnO) 2 ) Is a good and stable energy release material, and thus is widely applied to the field of batteries. But MnO inside the battery after the battery is used 2 Mainly generates manganese sesquioxide which is difficult to convert or recycle, and the prior art MnO 2 Is a one-time resource. China is a country with relatively deficient manganese resources and high-quality natural MnO 2 The number of the manganese-containing batteries is less and less, the issues of how to improve the energy replacement rate of the batteries, the unit capacity of the batteries and the like are very important, and the manganese-containing batteries play an important role in reducing the waste of natural manganese resources and protecting increasingly severe ecological environments.
At present, manganese dioxide is mainly used as the anode material of the water-based zinc ion secondary battery. However, the single-phase manganese dioxide material has poor conductivity and chemical stability, so that it is difficult to meet the commercial requirements of zinc ion batteries. The key problem of obtaining the high-performance zinc ion battery by improving the electrochemical performance of the anode material manganese dioxide.
The modification research on the manganese dioxide cathode material mainly focuses on the aspects of doping, compounding, carbon coating and the like, such as compounding manganese dioxide and vanadium pentoxide (CN 102683757A); manganese dioxide and carbon are compounded and carbon-nitrogen doped (CN 105390697A, CN107706405A and CN 108539163A). On the other hand, other patent reports of coated manganese dioxide materials are mainly applied to the fields of Microbial Fuel Cells (MFCs), supercapacitors, lithium ion battery negative electrode materials and the like.
MnO of anode material of current zinc ion battery 2 The main problems are:
1. during the charging and discharging process, the material has large volume change and the element manganese is dissolved, so that the cycling stability of the battery is poor;
2. the material has poor conductivity, so that the charge-discharge rate performance of the material is poor, and the further development of the material is hindered.
3、MnO 2 Has poor thermal stability, and has phase transition after exceeding 450 ℃, thereby limiting the application of various further heat treatment modifications.
In order to solve these problems, a commonly used modification method is to make the material into a nano-scale, on one hand, to reduce the particle size of the material to relieve the volume change of the material, and on the other hand, to improve the conductivity of the material by combining with a highly conductive carbon material (such as carbon nanotube, graphene, etc.), thereby improving the rate capability of the material. However, the process is complex, the preparation cost is high, and the industrialization is difficult.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a preparation method of a zinc salt mixed electrolyte and a manganese anode material for a zinc-manganese battery.
The technical scheme of the invention is as follows: a preparation method of a zinc-manganese battery comprises the following steps:
s1) preparation of high-performance zinc salt electrolyte
2mol L of -1 Zinc chloride and 1mol L -1 Dissolving ammonium chloride in distilled water, adding dilute acid to regulate pH valueObtaining zinc salt electrolyte with certain pH value;
s2), selecting one or more conductive carbon materials and adhesive and MnO in a certain mass ratio 2 Performing ball milling and mixing for a certain time to obtain a positive electrode material;
s3), the zinc-manganese button cell is assembled by using the zinc salt electrolyte in the step S1), the positive electrode material in the step S2) and the zinc-based material as a negative electrode material.
Further, in the step S1), the dilute acid is HCl or H 2 SO 4 、HNO 3 、CH 3 COOH、C 6 H 8 O 7 One or more of them.
Further, in the step S1), the pH value of the electrolyte adjusted by the dilute acid is 1.5-5.5.
Further, in the step S2), the conductive carbon material is one or a mixture of several of carbon nanotube CNT, acetylene black ACET and graphene oxide GO;
further, in the step S2), the binder is one or a mixture of polyvinyl alcohol PVA, polyvinyl pyrrolidone PVP, and polyethylene glycol PEG.
Further, in the step S2), the conductive carbon material of the positive electrode material accounts for 5-30% of the positive electrode material by mass.
Further, in the step S2), the binder of the positive electrode material accounts for 0.1-1.0% of the positive electrode material by mass.
Further, in the step S2), the ball milling time of the cathode material is 15-240min.
The invention also provides a preparation method of the zinc salt mixed electrolyte, which is characterized in that a certain amount of dilute acid is added into the zinc salt electrolyte to adjust the pH value of the electrolyte, and H in the electrolyte is increased + To promote Mn in the battery during charging and discharging 4+ /Mn 2+ The redox reaction occurs, thereby improving the electrochemical performance of the zinc-manganese battery.
Furthermore, the zinc salt electrolyte is prepared by dissolving a certain amount of zinc chloride and ammonium chloride in distilled water.
Further, the dilute acid is HCl and H 2 SO 4 、HNO 3 、CH 3 COOH、C 6 H 8 O 7 One or more of them.
Further, the pH value of the electrolyte adjusted by the dilute acid is 1.5-5.5.
The invention also provides a preparation method of the positive electrode material of the zinc-manganese battery, which selects one or more of the conductive carbon material and the binder and MnO 2 Ball milling and mixing are carried out, and the conductivity of the battery anode material is improved.
Further, the conductive carbon material is one or a mixture of CNT, ACET and GO.
Further, the binder is one or a mixture of more of PVA, PVP and PEG.
Further, the conductive carbon material of the positive electrode material accounts for 5-30% of the positive electrode material by mass.
Further, the mass of the binder of the positive electrode material accounts for 0.1-1.0% of the positive electrode material.
Further, the ball milling time of the anode material is 15-240min.
The invention has the beneficial effects that:
1. the invention selects one or more of conductive carbon material and binder and MnO 2 Ball milling and mixing are carried out, so that the conductivity of the battery anode material is obviously improved;
2. MnO formed by ball-milling and mixing anode material of the invention 2 The wettability is obviously improved, the electrolyte is favorably and fully soaked, and the phenomenon of potential difference caused by local unevenness after mixing is reduced, so that the electric energy loss of the battery due to self-discharge is reduced;
3. the electrolyte is simple in improvement method, and H in the electrolyte is obtained by adjusting the pH value of the zinc salt electrolyte + Can promote Mn in the battery in the charging and discharging process 4+ /Mn 2+ The redox reaction occurs, and the improved electrolyte has higher battery capacity and working voltage than the prior electrolyte under the condition of equal dischargeAll have showing and promote, and meanwhile, the discharge stability of battery is better, more is applicable to the high power battery.
4. The preparation method has the advantages of low energy consumption, low raw material price, simple operation, easy realization and realization of industrial production;
5. MnO of the present invention 2 The crystal form is good and uniform, the surface polarization of the material caused by the crystal form difference is reduced, simultaneously the discharge platform is improved, the discharge capacity is also obviously improved,
drawings
FIG. 1 shows MnO used in example 1 of the present invention 2 A Scanning Electron Microscope (SEM) image of the sample;
FIG. 2 shows the measured values at 50mV s in example 1 of the present invention -1 The cyclic voltammetry Curve (CV) measured by using the zinc-manganese button cell assembled by the electrolyte before and after the pH value is adjusted at the sweep rate of (1);
FIG. 3 shows the measured peak area at 10mAcm in example 1 of the present invention -2 The discharge curve graph (CP) of the zinc-manganese button cell assembled by using the electrolyte before and after the pH value is adjusted under the current density of (1);
fig. 4 is an Electrochemical Impedance Spectroscopy (EIS) of a zn-mn button cell assembled using electrolytes before and after pH adjustment in example 1 of the present invention;
FIG. 5 shows the measured peak value at 20mAcm in example 1 of the present invention -2 The cycle life of the zinc-manganese button battery assembled by using the electrolyte before and after the pH value is adjusted is 200 times of cycle life.
Detailed Description
The following further describes embodiments of the present invention in conjunction with the attached figures:
the reagents, methods and equipment adopted by the invention are conventional in the technical field.
Example 1
The embodiment provides a preparation method of a zinc-manganese battery, which includes:
s1) preparation of high-performance zinc salt electrolyte
2mol of L -1 Zinc chloride and 1mol L -1 Ammonium chloride dissolved in distilled water, 3mol L -1 Adjusting the pH value to 4.0 by HCl to prepare zinc salt electrolyte with the pH value;
s2) preparation of cathode material
Adding 15% of ACET, 1% of CNT and 0.5% of MnO of PVA based on the mass of the positive electrode material 2 Ball-milling and mixing for 60min to obtain the required anode material;
s3) assembling
The cathode material is manufactured into slurry and coated on a current collector to serve as a cathode, a commercial zinc-based material serves as a cathode, and the electrolyte is a zinc salt electrolyte with a pH value adjusted, and is assembled into a zinc-manganese button cell and marked as MOZ-H.
Comparative example:
and a control group is a zinc-manganese button cell assembled by using zinc salt electrolyte with unadjusted pH value, and the rest is the same as MOZ-H and is marked as MOZ.
Example 2
Performance testing of the batteries prepared in example 1
MnO used for the examples of the present invention 2 The sample was subjected to Scanning Electron Microscope (SEM) measurement, and as a result, mnO used was observed as shown in FIGS. 1 (a) and 1 (b) 2 The crystal form is good and uniform, and the surface polarization of the material caused by the crystal form difference is reduced.
As can be seen from the CV curve of FIG. 2, at 50mV s -1 Compared with MOZ, the capacity of MOZ-H is obviously improved.
From the CP curve of FIG. 3, it can be seen that at 10mAcm -2 Compared with MOZ, the MOZ-H discharge platform is improved, and the discharge capacity is obviously improved.
As can be seen from the EIS curve of FIG. 4, compared with MOZ, the conductivity of MOZ-H is significantly higher than that of MOZ, and the electrochemical performance of MOZ-H is also significantly improved.
As can be seen from the cycle life graph of FIG. 5, at 20mAcm -2 At a current density of (3), capacity of MOZ-H after 200 cycles, in comparison withThe retention rate is more than 88.7%, the capacity retention rate of MOZ is 66.2%, and the capacity retention rate of MOZ-H is obviously higher than that of MOZ.
In summary, the MnO 2 Ball-milling and mixing with conductive carbon material, binder and the like to be used as a positive electrode material, taking a commercial zinc-based material as a negative electrode, taking zinc salt electrolyte with certain pH value as the electrolyte, and assembling the zinc-manganese button cell with H in the zinc salt electrolyte + The discharge capacity and the stability of the lithium ion battery can be improved by increasing the amount of the lithium ion battery, and the lithium ion battery has a great application prospect.
Examples 3 to 20
The procedures of examples 3-20 were the same as in example 1, and the ACET content was 15% by mass of the positive electrode material, and 3mol L was used -1 The difference is the selection and the amount of the conductive carbon material except for the ACET and the binder in the positive electrode material, the ball milling time of the positive electrode material, and the difference of the acid and the pH selected in the zinc salt electrolyte, which is specifically shown in table 1.
TABLE 1 electrolyte compositions and Battery test results for examples 3-20
Wherein, examples 1, 3 and 4 show that the conductive carbon material selected by the anode material has great influence on the capacity of the zinc-manganese battery, examples 1, 5 and 6 show that CNTs with different mass ratios of the anode material have influence on the capacity of the zinc-manganese battery, examples 1, 7 and 8 show that the binder selected by the anode material has influence on the capacity of the zinc-manganese battery, examples 1, 9 and 10 show that PVA with different mass ratios of the anode material has influence on the capacity of the zinc-manganese battery, the anode material components 1, 11, 12 and 13 are the same, and the ball milling time has influence on the capacity of the zinc-manganese battery but has little difference. Examples 1, 14, 15, 16 and 17 illustrate that the difference in the addition of acid, even though the pH of the electrolyte is the same, has a large effect on the capacity of the zinc manganese cell. Examples 1, 18, 19 and 20 show that different pH values of the electrolyte have great influence on the capacity of the zinc-manganese battery, and the cathode material of the zinc-manganese battery with too low pH value has slight corrosion phenomenon. The performance of the zinc-manganese cell assembled using the examples 3-20 is inferior to that of the example 1.
The foregoing embodiments and description have been presented only to illustrate the principles and preferred embodiments of the invention, and various changes and modifications may be made therein without departing from the spirit and scope of the invention as hereinafter claimed.
Claims (10)
1. A preparation method of a zinc-manganese battery is characterized by comprising the following steps:
s1) preparation of high-performance zinc salt electrolyte
2mol L of -1 Zinc chloride and 1mol L -1 Dissolving ammonium chloride in distilled water, and then adding dilute acid to adjust the pH value to 1.5-5.5 to prepare zinc salt electrolyte with a certain pH value;
s2), selecting one or more conductive carbon materials and adhesive and MnO in a certain mass ratio 2 Performing ball milling and mixing for 15-240min to obtain a positive electrode material;
and S3), assembling the zinc-manganese button cell by using the zinc salt electrolyte in the step S1), the positive electrode material in the step S2) and the zinc-based material as negative electrode materials.
2. The method for preparing a zinc-manganese battery according to claim 1, characterized in that: in the step S1), the dilute acid is HCl or H 2 SO 4 、HNO 3 、CH 3 COOH、C 6 H 8 O 7 One or more of them.
3. The method for preparing a zinc-manganese battery according to claim 1, characterized in that: in the step S2), the conductive carbon material is one or a mixture of carbon nano tube CNT, acetylene black ACET and graphene oxide GO;
the binder is one or a mixture of polyvinyl alcohol PVA, polyvinylpyrrolidone PVP and polyethylene glycol PEG.
4. The method for preparing a zinc-manganese battery according to claim 1, characterized in that: in the step S2), the conductive carbon material of the anode material accounts for 5-30% of the mass of the anode material;
the mass of the binder of the positive electrode material accounts for 0.1-1.0% of the positive electrode material.
5. The preparation method of the zinc salt mixed electrolyte is characterized in that a certain amount of dilute acid is added into the zinc salt electrolyte to adjust the pH value of the electrolyte to be 1.5-5.5, and H in the electrolyte is increased + To promote Mn in the battery during charging and discharging 4+ /Mn 2+ The redox reaction occurs, thereby improving the electrochemical performance of the zinc-manganese battery.
6. The method for preparing the zinc salt mixed electrolyte according to claim 5, wherein the zinc salt electrolyte is 2mol L -1 Zinc chloride and 1mol L -1 The ammonium chloride is prepared by dissolving in distilled water.
7. The method for preparing zinc salt mixed electrolyte according to claim 5, wherein the dilute acid is HCl or H 2 SO 4 、HNO 3 、CH 3 COOH、C 6 H 8 O 7 One or more of them.
8. The preparation method of the positive electrode material of the zinc-manganese battery is characterized in that the method selects one or more of a conductive carbon material and a binder and MnO 2 Ball milling and mixing are carried out for 15-240min, and the conductivity of the battery anode material is improved.
9. The method for preparing the positive electrode material of the zinc-manganese battery according to claim 8, wherein the conductive carbon material is one or a mixture of Carbon Nanotubes (CNT), acetylene black ACET and Graphene Oxide (GO);
the binder is one or a mixture of polyvinyl alcohol PVA, polyvinylpyrrolidone PVP and polyethylene glycol PEG.
10. The preparation method of the positive electrode material of the zinc-manganese battery according to claim 7, wherein the conductive carbon material of the positive electrode material accounts for 5-30% of the mass of the positive electrode material;
the mass of the binder of the positive electrode material accounts for 0.1-1.0% of that of the positive electrode material.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113097518A (en) * | 2021-03-18 | 2021-07-09 | 苏州柔能纳米科技有限公司 | Electrolyte for flexible neutral zinc-manganese dioxide battery and preparation method thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BE746333A (en) * | 1969-02-20 | 1970-08-20 | Union Carbide Corp | BATTERY CONSTRUCTION |
| US4361633A (en) * | 1981-08-24 | 1982-11-30 | Polaroid Corporation | Laminar electrical cells and batteries |
| JPS61107665A (en) * | 1984-10-29 | 1986-05-26 | Hitachi Maxell Ltd | Manufacture of dry battery |
| CN1112737A (en) * | 1994-03-09 | 1995-11-29 | 电池技术公司 | High capacity rechargeable cell having manganese dioxide electrode |
| CN1260603A (en) * | 1999-11-01 | 2000-07-19 | 卢大伟 | Zinc-manganese battery |
| CN101502817A (en) * | 2009-02-19 | 2009-08-12 | 中银（宁波）电池有限公司 | Planetary type ball-milling treatment for preparing electrolytic manganese dioxide |
| CN102856557A (en) * | 2012-09-20 | 2013-01-02 | 威海至圣电池科技有限公司 | Novel battery |
-
2020
- 2020-12-01 CN CN202011388559.8A patent/CN112490458A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BE746333A (en) * | 1969-02-20 | 1970-08-20 | Union Carbide Corp | BATTERY CONSTRUCTION |
| US4361633A (en) * | 1981-08-24 | 1982-11-30 | Polaroid Corporation | Laminar electrical cells and batteries |
| JPS61107665A (en) * | 1984-10-29 | 1986-05-26 | Hitachi Maxell Ltd | Manufacture of dry battery |
| CN1112737A (en) * | 1994-03-09 | 1995-11-29 | 电池技术公司 | High capacity rechargeable cell having manganese dioxide electrode |
| CN1260603A (en) * | 1999-11-01 | 2000-07-19 | 卢大伟 | Zinc-manganese battery |
| CN101502817A (en) * | 2009-02-19 | 2009-08-12 | 中银（宁波）电池有限公司 | Planetary type ball-milling treatment for preparing electrolytic manganese dioxide |
| CN102856557A (en) * | 2012-09-20 | 2013-01-02 | 威海至圣电池科技有限公司 | Novel battery |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113097518A (en) * | 2021-03-18 | 2021-07-09 | 苏州柔能纳米科技有限公司 | Electrolyte for flexible neutral zinc-manganese dioxide battery and preparation method thereof |
| CN113097518B (en) * | 2021-03-18 | 2024-06-04 | 苏州柔能纳米科技有限公司 | Electrolyte for flexible neutral zinc-manganese battery and preparation method thereof |
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Application publication date: 20210312 |