CN104882570B - Steel shell of alkaline zinc-manganese battery and alkaline zinc-manganese battery - Google Patents
Steel shell of alkaline zinc-manganese battery and alkaline zinc-manganese battery Download PDFInfo
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- CN104882570B CN104882570B CN201510320168.5A CN201510320168A CN104882570B CN 104882570 B CN104882570 B CN 104882570B CN 201510320168 A CN201510320168 A CN 201510320168A CN 104882570 B CN104882570 B CN 104882570B
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- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 153
- 239000010959 steel Substances 0.000 title claims abstract description 153
- WJZHMLNIAZSFDO-UHFFFAOYSA-N manganese zinc Chemical compound [Mn].[Zn] WJZHMLNIAZSFDO-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 238000000576 coating method Methods 0.000 claims abstract description 114
- 239000011248 coating agent Substances 0.000 claims abstract description 112
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 88
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 67
- 238000000034 method Methods 0.000 claims description 21
- 239000000463 material Substances 0.000 claims description 19
- 239000011230 binding agent Substances 0.000 claims description 18
- 239000011268 mixed slurry Substances 0.000 claims description 15
- 239000006258 conductive agent Substances 0.000 claims description 10
- 238000005507 spraying Methods 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 8
- 238000002360 preparation method Methods 0.000 claims description 7
- 239000006230 acetylene black Substances 0.000 claims description 6
- 239000002033 PVDF binder Substances 0.000 claims description 5
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 4
- 238000011065 in-situ storage Methods 0.000 claims description 3
- 238000000053 physical method Methods 0.000 claims description 3
- 230000002829 reductive effect Effects 0.000 abstract description 24
- 239000003575 carbonaceous material Substances 0.000 description 16
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 14
- 230000009467 reduction Effects 0.000 description 11
- 238000007789 sealing Methods 0.000 description 10
- 229910002804 graphite Inorganic materials 0.000 description 9
- 239000010439 graphite Substances 0.000 description 9
- 239000013543 active substance Substances 0.000 description 7
- 229910052759 nickel Inorganic materials 0.000 description 7
- 238000003860 storage Methods 0.000 description 7
- SZKTYYIADWRVSA-UHFFFAOYSA-N zinc manganese(2+) oxygen(2-) Chemical compound [O--].[O--].[Mn++].[Zn++] SZKTYYIADWRVSA-UHFFFAOYSA-N 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 238000005260 corrosion Methods 0.000 description 6
- 230000007797 corrosion Effects 0.000 description 6
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
- 239000001768 carboxy methyl cellulose Substances 0.000 description 5
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 5
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 5
- 229940105329 carboxymethylcellulose Drugs 0.000 description 5
- 229910052802 copper Inorganic materials 0.000 description 5
- 239000010949 copper Substances 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 5
- 238000009713 electroplating Methods 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
- 229920003048 styrene butadiene rubber Polymers 0.000 description 5
- 239000002174 Styrene-butadiene Substances 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 4
- 239000006229 carbon black Substances 0.000 description 4
- 239000002270 dispersing agent Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000007493 shaping process Methods 0.000 description 4
- 238000001132 ultrasonic dispersion Methods 0.000 description 4
- RNWHGQJWIACOKP-UHFFFAOYSA-N zinc;oxygen(2-) Chemical compound [O-2].[Zn+2] RNWHGQJWIACOKP-UHFFFAOYSA-N 0.000 description 4
- 229920000049 Carbon (fiber) Polymers 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 239000011149 active material Substances 0.000 description 3
- 229910003481 amorphous carbon Inorganic materials 0.000 description 3
- 239000004917 carbon fiber Substances 0.000 description 3
- 229910021393 carbon nanotube Inorganic materials 0.000 description 3
- 239000002041 carbon nanotube Substances 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 3
- 238000004080 punching Methods 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 239000002518 antifoaming agent Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000006056 electrooxidation reaction Methods 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000007740 vapor deposition Methods 0.000 description 2
- 235000014692 zinc oxide Nutrition 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- 241000446313 Lamella Species 0.000 description 1
- 229910003174 MnOOH Inorganic materials 0.000 description 1
- 241000221535 Pucciniales Species 0.000 description 1
- 241000872198 Serjania polyphylla Species 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 238000010009 beating Methods 0.000 description 1
- 239000007767 bonding agent Substances 0.000 description 1
- 229940105847 calamine Drugs 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 239000002482 conductive additive Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 238000013401 experimental design Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 229910052864 hemimorphite Inorganic materials 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920005596 polymer binder Polymers 0.000 description 1
- 239000002491 polymer binding agent Substances 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007790 scraping Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- CPYIZQLXMGRKSW-UHFFFAOYSA-N zinc;iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Fe+3].[Fe+3].[Zn+2] CPYIZQLXMGRKSW-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/10—Primary casings; Jackets or wrappings
- H01M50/116—Primary casings; Jackets or wrappings characterised by the material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/10—Primary casings; Jackets or wrappings
- H01M50/116—Primary casings; Jackets or wrappings characterised by the material
- H01M50/124—Primary casings; Jackets or wrappings characterised by the material having a layered structure
-
- 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)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Primary Cells (AREA)
- Sealing Battery Cases Or Jackets (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a steel shell of an alkaline zinc-manganese battery, which comprises a current collector steel shell, wherein the inner wall of the current collector steel shell is coated with a graphene modified conductive coating; the thickness of the conductive coating is 0.01-20 microns, so that the covering density and the bonding performance of the conductive coating and the inner surface of the steel shell are improved, the radial resistance of the battery and the interface resistance between the anode ring and the steel shell are reduced, and the high-current discharge performance of the alkaline zinc-manganese battery is further improved.
Description
Technical Field
The invention relates to the technical field of conductive coatings for steel shells of alkaline zinc-manganese batteries, in particular to a steel shell of an alkaline zinc-manganese battery.
Background
The alkaline zinc-manganese dioxide battery mainly comprises a negative electrode, diaphragm paper, electrolyte and a shell; the negative electrode of the alkaline zinc-manganese battery is mainly a slurry mixture prepared by zinc powder, a water-absorbing polymer as a gel and KOH dissolved with ZnO as electrolyte. The anode is mainly manganese dioxide (MnO 2), graphite, a proper amount of adhesive or release agent and KOH electrolyte are added, and the mixture is uniformly mixed, and is subjected to tabletting, granulation and ring beating to prepare the anode mixture with the ring structure. The diaphragm paper is a special porous membrane, and the electrolyte is made of KOH solution. The shell is a sealing device formed by a negative pole bottom, a sealing ring and a steel shell.
The steel shell of the alkaline zinc-manganese dioxide battery is different from other batteries, and is a container of the battery, and is a positive current collector: the active material is uniformly distributed on the surface of the steel shell current collector, and the current collector collects electrons generated by electrochemical reaction through physical contact with the active material and guides the collected electrons out of an external circuit, so that the process of converting chemical energy into electric energy is realized. The contact between the current collector and the active material is an important influence factor on the discharge performance of the alkaline zinc-manganese battery. Because the nickel coating mouth that the blind hole electroplating is thick end thin, cause the inner chamber size of oral area to be less than the inner chamber size of bottom, consequently even the size of positive polar ring is the same completely, the ring is respectively also different with the steel casing cooperation degree of oral area and bottom. The influence of the steel shell on the high-current discharge performance of the battery is mainly caused by the treatment condition of the inner surface of the steel shell, and the conductive coating on the inner wall of the steel shell can improve the matching uniformity and the conductivity of the ring and the shell, so that the steel shell is an important means for improving the utilization rate of the positive active material and the high-current discharge performance of the battery. In addition, in the existing steel shell electroplating production process, electroplating pinholes exist at the opening part and the bottom part, and particularly, the bottom part even has a bottom leakage phenomenon to expose the iron matrix. Because the potential of MnO2 is positive (phi oMnO2/MnOOH = 0.415V) and the potential of the nickel coating on the inner surface of the steel shell, particularly the steel shell substrate is negative (phi oFe/Fe (OH) 3= -0.89V), the inner surface of the steel shell is subjected to chemical and electrochemical oxidation of a positive electrode substance, so that the nickel coating is oxidized and the substrate (a pinhole, an exposed bottom or a torn part) is oxidized. The common phenomenon is that the inner surface of the steel shell is provided with pockmarks or rusts, so that the conductivity of the steel shell is reduced, the current collection effect on the positive electrode is further influenced, and the storage and discharge performance of the battery is reduced. A conductive coating is coated on the inner wall of the steel shell, and the steel shell can be mechanically isolated from the anode, so that the chemical and electrochemical oxidation of the anode material MnO2 on the steel shell can be prevented or relieved.
The conductive coating is obtained by spraying conductive coating on the inner wall of the steel shell, and no conductive coating specially designed for the alkaline zinc-manganese battery exists at present. The current conductive coating is mainly selected from graphite or carbon black with good conductivity as a carbon material of the conductive coating from the comprehensive consideration of conductivity and cost, such as enterprises of Qingdao Tianrun, germany Hangao, japanese Zhao and electrician, shanghai Zhongxing Pai and the like. We found through a large number of experiments: in order to meet the requirements of corrosion resistance and oxidation resistance of the inner surface of the steel shell, the thickness of the coating is not less than 5-50 mu m when the conductive coating of the manufacturer is adopted, so that the internal resistance of the battery is increased, and the capacity of the battery is reduced; due to the use of a hydrophobic protective film on the inner surface of the steel shell, the long-time storage of the battery and the reduction of the adhesive property of a polymer binder, the adhesion between the common carbon material-based conductive coating and the steel shell is gradually reduced, the conductive coating absorbs liquid to generate irreversible expansion, the conductive coating falls off to further increase the interface resistance, and the storage discharge of each item of the battery is obviously reduced, so that the internal resistance of the battery is increased by 3-4 times and the high-current discharge performance of the alkaline manganese battery produced by common manufacturers is reduced by 30-50 percent within 3-4 years of the shelf life.
In a word, the current coating/coating taking graphite or carbon black as a conductive matrix is widely used for the steel shell of the alkaline manganese battery, but we find that the coating/coating has limited covering density and protective capacity on the inner surface of the steel shell, and needs higher thickness, while higher coating thickness (5-50 μm) causes the increase of radial resistance of the steel shell and the reduction of battery capacity, and meanwhile, the adhesion performance of the conductive coating to the steel shell is reduced, and finally, the large-current discharge performance and storage performance of the battery are reduced, so that the coating/coating is not suitable for the development requirement of the current novel digital electrical appliance products, and the further expansion of the market of the alkaline zinc-manganese battery is greatly restricted. The field lacks a technology for improving the conductive coating on the inner wall of the steel shell, which can improve the heavy-current discharge and storage performance of the alkaline zinc-manganese battery, and the field urgently needs to develop the technology which can greatly improve the heavy-current discharge and storage performance of the alkaline zinc-manganese battery.
According to the invention, a novel conductive material with a two-dimensional nanostructure, namely graphene, is adopted, and analysis of the structure and physical properties shows that the graphene modified conductive coating has higher conductive performance, and in addition, the graphene modified conductive coating has the advantages that due to the special lamella and the high-defect high-functional group structure, when the material is used for modifying the inner surface of a steel shell, the covering density and the adhesion performance of the conductive coating on the inner surface of the steel shell are greatly improved (as shown in figure 1), the corrosion and rusting of the steel shell caused by low covering density or expansion stripping of the conventional carbon material coating can be effectively inhibited, the thickness of the coating is only required to be 0.01-20 mu m, the capacity is not lost, the conductive performance is also improved, the interface resistance and the radial resistance between a positive electrode ring and the steel shell are reduced, the positive electrode active substance and the capacity of the alkaline zinc-manganese battery are better exerted, and the high-current discharge performance of the alkaline zinc-manganese battery is improved.
Disclosure of Invention
The invention aims to provide a steel shell of an alkaline zinc-manganese battery, which can improve the covering density and the bonding performance of a conductive coating and the inner surface of the steel shell, reduce the radial resistance of the battery and the interface resistance between an anode ring and the steel shell, and further improve the heavy-current discharge performance of the alkaline zinc-manganese battery.
The technical scheme adopted by the invention for solving the technical problems is as follows:
the steel shell of the alkaline zinc-manganese battery is characterized by comprising a current collector steel shell, wherein the inner wall of the current collector steel shell is coated with a graphene modified conductive coating; the thickness of the conductive coating is 0.01 to 20 microns.
The conductive coating comprises the following substances in parts by mass: 1-98 parts of graphene material, 1-98 parts of conductive agent and 1-10 parts of binder.
The graphene is prepared by a graphite oxide reduction method, a physical method, a mechanical stripping method, an epitaxial growth method, a vapor deposition method or an in-situ self-generated template method.
The thickness of the graphene material is 0.5-100 nanometers.
The specific surface area of the graphene material is 10-2500 square meters per gram.
The area of the graphene material is 0.01-1000 mu m.
The conductive agent comprises one or a combination of more of graphite, carbon nano tubes, carbon fibers, activated carbon, amorphous carbon, conductive carbon black, acetylene black, super-Li and KS-6; the binder comprises one or a combination of polyvinylidene fluoride, CMC, SBR and LA series binders.
The preparation method of the conductive coating comprises the following steps:
(a) Uniformly dispersing graphene, a conductive agent, a binder and a small amount of additives in a solvent to obtain mixed slurry;
(b) And spraying the mixed slurry on the inner wall of a steel shell, and then drying to obtain the graphene modified conductive coating. The additive comprises one or more of a stabilizer, a neutralizer and a defoaming agent.
Compared with the prior art, the invention has the advantages that: 1. due to the punching and electroplating of the steel shell, certain roughness exists on the inner surface, and the flexibility of the graphene is favorable for the adhesion of the conductive coating and the uneven surface of the inner wall of the steel shell.
2. The covering density of the conductive coating on the inner surface of the steel shell is lower due to the limitation of the particle size of the conventional carbon material, but the invention unexpectedly discovers that the graphene is used as the conductive coating to modify the inner surface of the steel shell, and the covering density of the conductive coating on the inner surface of the steel shell is greatly improved due to the special lamellar two-dimensional structure of the graphene, so that the corrosion and the rusting of the steel shell and the performance reduction of a battery, which are generated due to the low covering density of the conventional carbon material coating, can be effectively inhibited;
3. the invention finds that the characteristic of the graphene can realize that the coating forms good compatibility and wettability on the surface of a metal steel shell with higher surface energy according to the similar compatibility principle, and can improve the close fit between a conductive film and the steel shell from the physical perspective;
4. the graphene surface has a large number of functional groups, and the invention unexpectedly discovers that O atoms, N atoms or S atoms in the graphene surface have chemical reaction with the surface of the steel shell, so that the connection of chemical bonds is generated, the bonding performance of the conductive film and the metal steel shell is improved from the chemical perspective, the chemical adhesion has higher strength, and the expansion stripping of the conventional carbon material coating caused by water absorption of the conductive coating and over discharge of a battery can be effectively inhibited;
5. in the ring embedding process, an axial shearing force can be generated on the conductive coating when the positive ring in interference fit is embedded, the conventional conductive coating is not tightly combined with the inner wall of the steel shell, the surface of the granular carbon material coating is uneven, and obvious secondary destructiveness can be generated on the conductive film in the positive ring embedding process, so that part of the coating is scraped. The graphene modified conductive coating has good adhesion force with the steel shell, and the surface of the two-dimensional flaky graphene is smooth and flat, so that the scraping amount of the anode ring is remarkably reduced;
6. the graphene has extremely high electronic conductivity, and due to the good bonding property between the graphene modified coating and the steel shell, experiments prove that the dosage of an organic insulating binder in the conductive coating can be reduced, so that the electronic conductivity of the conductive coating is improved, and the axial resistance of the related conductive coating is reduced;
7. on the premise of ensuring the covering density, the thickness of the coating only needs to be 0.01-20 mu m, and the radial resistance of the conductive coating modified steel shell is effectively reduced;
8. the contact between the conventional carbon material particles and the rigid surface of the steel shell is point-surface contact, the effective interface contact area of the conventional carbon material particles and the rigid surface of the steel shell is limited, the interface resistance is large, and the fact that the point-surface contact between the conventional conductive agent-based conductive coating and the inner wall of the steel shell is improved into surface-surface contact by the graphene is found, the effective contact area is remarkably improved, and the interface resistance between the steel shell and the conductive film is greatly reduced;
9. as a positive current collector, the graphene modified coating improves the conductivity of the steel shell and the uniformity of the surface property of the inner wall of the steel shell, improves the current collection effect of the positive electrode and the resistance distribution in the positive electrode area, further influences the current potential distribution and the reduction of the discharge performance resistance, is beneficial to better exerting the positive active substance and capacity of the alkaline zinc-manganese battery, and improves the large-current discharge performance and the discharge performance of a high-voltage section of the alkaline zinc-manganese battery;
10. the thickness of the coating is reduced, so that the filling amount of the active substance can be properly increased on the premise of a certain inner diameter of the steel shell, and the capacity of the battery is increased;
drawings
FIG. 1 is a schematic view of a prior art coated steel shell construction;
FIG. 2 is a schematic view of the coated steel can of the present invention;
FIG. 3 is a voltage division curve of 1.5W/0.65W,2s/28s,5m/h,24h/d for the alkaline zinc-manganese battery;
FIG. 4 is a voltage division curve of 1000mA,10s/m,1h/d for an alkaline zinc-manganese dioxide battery.
FIG. 1 is a conventional conductive coating; 2 is a conventional steel shell; 3, a graphene conductive coating; 4, a steel shell.
Detailed Description
The invention is described in further detail below with reference to the following examples of the drawings.
The inventor of the invention has made extensive and intensive studies, and unexpectedly obtained a technique capable of effectively inhibiting the corrosion and rust of a steel shell and the reduction of battery performance caused by the expansion peeling of a conventional conductive coating and the low covering density, or the limitation of higher internal resistance of a battery caused by the necessary high thickness of the conventional conductive coating by improving a preparation process, so that the interface resistance and the radial resistance between an anode ring and the steel shell can be reduced, the utilization rate of an anode active substance and the short-circuit current of an alkaline zinc-manganese battery can be improved, and the high-voltage end discharge of the battery can be prolonged, thereby completing the invention.
The technical concept of the invention is as follows:
the inventor aims at the limitation of the conventional coating, the covering density of the conductive coating on the inner surface of the steel shell is lower, and the higher thickness of the conductive coating can cause the increase of the internal resistance and the reduction of the capacity of the battery; the adhesion between the common carbon material conductive coating and the steel shell can be gradually reduced, and the conductive coating falls off to cause the reduction of various storage discharge of the battery, and the like, thereby providing a steel shell coating modification technology for the alkaline zinc-manganese battery. The inventor finds that if the graphene modified conductive coating is adopted, the graphene has a special lamellar two-dimensional structure, the adhesion performance and the covering density of the conductive coating and the inner surface of the steel shell are greatly improved by using the material to modify the inner surface of the steel shell, the corrosion and rust of the steel shell and the performance reduction of the battery, which are generated by the expansion stripping and the low covering density of the conventional carbon material coating, can be effectively inhibited, the coating thickness only needs to be 0.01-20 mu m, the conductive performance can be improved under the condition of no capacity loss, the interface resistance and the radial resistance between the anode ring and the steel shell are reduced, the anode active substance and the capacity of the alkaline zinc-manganese battery are better exerted, and the high-current discharge performance of the alkaline zinc-manganese battery is improved.
Unless otherwise specified, the various starting materials of the present invention are commercially available; or prepared according to conventional methods in the art. Unless defined or stated otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In addition, any methods and materials similar or equivalent to those described herein can be used in the methods of the present invention.
Steel shell of alkaline zinc-manganese battery and preparation method thereof
The steel shell of the alkaline zinc-manganese dioxide battery is modified by a graphene coating, and the preparation method comprises the following steps:
a, providing a steel shell;
the steel shell can be a nickel pre-plated steel shell or a nickel post-plated steel shell and is punched by a steel strip; the nickel pre-plated steel shell is prepared by firstly plating nickel on a steel strip, punching the steel strip into an open steel shell with a fixed shape and then cleaning the steel shell; punching the steel strip into an open steel shell with a fixed shape by using a nickel-plated steel shell as a line, and then removing oil, electroplating and cleaning to obtain the nickel-plated steel shell; the invention has no specific requirements on the type and shape of the steel shell as long as the invention purpose is not limited;
uniformly dispersing graphene, a conventional conductive agent, a binder and a small amount of additives such as a stabilizer, a neutralizer and a defoaming agent in a solvent to obtain mixed slurry;
the conventional conductive additive comprises one or a combination of more of graphite, carbon nano tubes, carbon fibers, activated carbon, amorphous carbon, conductive carbon black, acetylene black, super-Li and KS-6; the binder comprises one or a combination of polyvinylidene fluoride, CMC, SBR and LA series binders; the solvent can be organic solvent such as butanone or pure water; the present invention has no particular requirements for the conventional conductive agent, binder and additive or solvent as long as the object of the present invention is not limited;
c, spraying and drying the mixed slurry on the inner wall of a steel shell to finally obtain the graphene coating modified steel shell of the alkaline zinc-manganese dioxide battery;
the mixed slurry preparation process, the spraying and drying process are known to those skilled in the art, and there is no particular requirement as long as the object of the present invention is not limited.
Alkaline zinc-manganese battery
The invention also provides an alkaline zinc-manganese battery containing the graphene coating modified steel shell. The alkaline zinc-manganese cell may contain other allowable components such as seal rings, copper pins and negative electrode pads, calamine negative electrodes, positive electrodes, electrolyte, separator paper, etc. These components are not specifically required and are known to those skilled in the art as long as they do not limit the object of the present invention.
Compared with the steel shell of the existing various alkaline zinc-manganese batteries, the invention is characterized in that: 1. the steel shell of the alkaline zinc-manganese dioxide battery is added with graphene with ultrahigh conductivity, ultrahigh flexibility and ultrathin two-dimensional lamellar structure besides conventional carbon materials;
2. the graphene modified steel shell is more beneficial to covering and adhering the inner surface of the steel shell than the common conductive coating modified steel shell, and can effectively inhibit the corrosion and rusting of the steel shell and the performance reduction of a battery caused by low covering density or expansion stripping of a conventional carbon material coating;
3. the graphene modified steel shell inner wall coating improves the conductivity, reduces the interface resistance and the radial resistance between the positive electrode ring and the steel shell, better exerts the positive electrode active substance and the capacity of the alkaline zinc-manganese battery, improves the heavy current discharge performance of the alkaline zinc-manganese battery, and has more advantages compared with other coatings;
4. by adjusting the proportion of the graphene to the conventional carbon material in the conductive coating, the alkaline zinc-manganese battery steel shell which is most suitable for discharge and cost can be obtained, and then the alkaline zinc-manganese battery can be obtained;
5. the preparation method is simple and easy to implement, the materials are easy to obtain, the graphene consumption is low, only slight adjustment is needed on the mature production line of the alkaline zinc-manganese battery, and the method is suitable for large-scale industrial production.
Other aspects of the invention will be apparent to those skilled in the art in view of the disclosure herein.
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. The experimental procedures, in which specific conditions are not specified, in the following examples are generally carried out according to conventional conditions or according to conditions recommended by the manufacturers.
Unless defined or stated otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In addition, any methods and materials similar or equivalent to those described herein can be used in the methods of the present invention.
To further illustrate the contents, essential features and significant advances of the present invention, the following comparative examples and examples are described in detail below, but not limited to the examples.
As shown in fig. 1, due to the limitation of the particle size of the conventional carbon material, the coverage density of the conventional coating on the surface of the steel shell is low, and uncovered pinholes exist; in order to improve the coverage rate, the coating thickness can only be increased, the thickness of the conductive coating is generally 5-50 mu m, so that the radial resistance of the steel shell is increased, the energy density of the battery is limited, and the contact between the conventional carbon material and the inner surface of the steel shell is point-to-surface contact, so that the effective contact area is lost to a certain extent. As shown in fig. 2, the covering density of the graphene with the two-dimensional sheet structure in the graphene modified coating on the surface of the steel shell is obviously improved, the thickness of the coating is reduced, the graphene is in face-to-face contact with the inner surface of the steel shell, and the effective area of conductive contact is fully increased.
Comparative example 1:
dispersing 84wt% of carbon black, 15wt% of CMC binder and 1wt% of dispersant sodium dodecyl sulfate in water, and performing ultrasonic dispersion to obtain mixed slurry; spraying and drying the mixed slurry on the inner wall of a steel shell to finally obtain the steel shell of the conventional coating modified alkaline zinc-manganese battery, wherein the thickness of the coating of the steel shell is 10 mu m;
then embedding the positive ring into the steel shell, inserting the diaphragm paper, injecting the zinc paste, inserting the current collector consisting of the copper nail, the negative electrode bottom and the sealing ring, curling, shaping and sealing to obtain the LR6 battery, testing the high-current discharge performance of the LR6 battery by using the DM-2000 primary battery performance testing system, and testing the short-circuit current of the battery, wherein the results are shown in the following table 1.
In order to verify the influence of the modification of the conductive coating on the protection capability and the conductivity of the steel shell and to facilitate the research, the improved resistance of the steel shell is divided into a radial resistance and an axial resistance. The radial resistance refers to the resistance along the radius direction of the steel shell, and mainly reflects the resistance between the inner surface of the steel shell and a contact object of the steel shell in experimental design, and can be called interface resistance; the axial resistance refers to the resistance of the steel shell parallel to the central axis, if the steel shell is regarded as an infinite thin plane, the resistance can be called the surface resistance of the steel shell, the change of the resistance mainly reflects the intrinsic conductivity of the conductive coating, and the change of the internal surface property of the steel shell after the conductive coating is modified is judged by measuring the change of the resistance of the steel shell. During measurement, the steel shell is divided into two parts to realize measurement of two resistances, and due to the property difference between different steel shells and the possible thickness difference of a coating layer, the result is the average value of multiple experiments. The results are shown in Table 2.
Example 1
Obtaining a graphene material by a graphite oxide reduction method, wherein the thickness of the graphene material is 10 nanometers, the specific surface area is 2500 square meters per gram, and the area is 0.01 micrometer, dispersing 49wt% of graphene, 50wt% of carbon black, 1wt% of CMC (carboxy methyl cellulose) binder and a small amount of dispersant sodium dodecyl sulfate in water, and performing ultrasonic dispersion to obtain a mixed slurry; spraying and drying the mixed slurry on the inner wall of a steel shell to finally obtain the steel shell of the alkaline zinc-manganese battery with the graphene modified conductive coating, wherein the loading amount of the graphene modified coating of the steel shell is 0.6 mg/cell, and the thickness of the conductive coating is 1 micron; and then embedding the positive electrode ring into the steel shell, inserting the diaphragm paper, injecting zinc paste, inserting a current collector consisting of a copper nail, a negative electrode bottom and a sealing ring, and curling, shaping and sealing to obtain the LR6 battery. The test method is the same as that of comparative example 1, and the results are shown in tables 1 and 2. The conductive agent comprises one or more of graphite, carbon nano tubes, carbon fibers, activated carbon, amorphous carbon, conductive carbon black, acetylene black, super-Li and KS-6, and the binder can also be one or more of polyvinylidene fluoride, SBR and LA series binders.
Example 2
Obtaining a graphene material by a physical method, wherein the thickness of the graphene material is 100 nanometers, the specific surface area is 10 square meters per gram, the area is 10 micrometers, 98wt% of graphene, 1wt% of acetylene black, 1wt% of polyvinylidene fluoride binder and a small amount of dispersant sodium dodecyl sulfate are dispersed in water, and mixed slurry is obtained by ultrasonic dispersion; spraying and drying the mixed slurry on the inner wall of a steel shell to finally obtain the steel shell of the alkaline zinc-manganese battery with the graphene modified conductive coating, wherein the thickness of the conductive coating is 20 micrometers; and then embedding the positive electrode ring into the steel shell, inserting the diaphragm paper, injecting zinc paste, inserting a current collector consisting of a copper nail, a negative electrode bottom and a sealing ring, and curling, shaping and sealing to obtain the LR6 battery. The test method is the same as that of comparative example 1, and the results are shown in tables 1 and 2.
Example 3
Obtaining a graphene material by a vapor deposition method, wherein the thickness of the graphene material is 0.5 nanometer, the specific surface area is 1250 square meters per gram, and the area is 1000 micrometers, dispersing 1wt% of graphene, 89wt% of graphite, 10wt% of SBR (styrene butadiene rubber) binder and a small amount of dispersant sodium dodecyl sulfate into water, and performing ultrasonic dispersion to obtain a mixed slurry; spraying and drying the mixed slurry on the inner wall of a steel shell to finally obtain the steel shell of the graphene modified conductive coating of the alkaline zinc-manganese dioxide battery, wherein the thickness of the conductive coating is 0.01 micrometer; and then embedding the positive electrode ring into the steel shell, inserting the diaphragm paper, injecting zinc paste, inserting a current collector consisting of a copper nail, a negative electrode bottom and a sealing ring, and curling, shaping and sealing to obtain the LR6 battery. Graphene can also be prepared by mechanical lift-off, epitaxial growth and in-situ template methods.
The test method is the same as that of comparative example 1, and the results are shown in tables 1 and 2.
Table 1 comparison of the discharge performance at high current and the short-circuit current of the alkaline zinc-manganese battery before and after the graphene coating modified steel can of the present invention
Through the experiments in table 1, it can be found that the new formulation process of the invention can improve the discharge performance of large current or high power, and the short-circuit current is also obviously improved. The graphene coating has higher covering density on the steel shell, is more beneficial to improving the contact between the positive electrode ring and the steel shell, reduces the resistance, is beneficial to better exerting the positive electrode active substance and the capacity of the alkaline zinc-manganese battery, and improves the heavy current discharge performance and the discharge of a high-voltage section of the alkaline zinc-manganese battery.
Table 2 comparison of axial resistance and radial resistance of steel cases before and after modification of the steel case with graphene coating according to the present invention
| Radial resistance | Axial resistance | |
| Comparative example 1 | 0.6 ohm | 1.4 ohm |
| Example 1 | 0.3 ohm | 0.5 ohm |
| Example 2 | 0.25 ohm | 0.6 ohm |
| Example 3 | 0.2 ohm | 0.4 ohm |
The graphene has extremely high electronic conductivity, and due to the good bonding property between the graphene modified coating and the steel shell, the using amount of an organic insulating bonding agent in the conductive coating can be effectively reduced, so that the electronic conductivity of the conductive coating is improved, and the axial resistance of the related conductive coating is reduced; the graphene improves the point-surface contact between the conventional conductive agent-based conductive coating and the inner wall of the steel shell into surface-surface contact, so that the effective contact area is remarkably increased, and in addition, on the premise of ensuring the covering density, the thickness of the coating only needs to be 0.01-20 mu m, so that the interface resistance between the steel shell and the conductive film is greatly reduced, and further the radial resistance is also reduced.
The foregoing is merely a preferred embodiment of the invention and is not intended to limit the scope of the invention, which is defined by the claims appended hereto, and any other technical entity or method that is encompassed by the claims as broadly defined herein, or equivalent variations thereof, is contemplated as being encompassed by the claims.
All documents referred to herein are incorporated by reference into this application as if each were individually incorporated by reference. Furthermore, it should be understood that various changes and modifications can be made by those skilled in the art after reading the above disclosure, and equivalents also fall within the scope of the invention as defined by the appended claims.
Claims (2)
1. The steel shell of the alkaline zinc-manganese battery is characterized by comprising a current collector steel shell, wherein the inner wall of the current collector steel shell is coated with a graphene modified conductive coating; the thickness of the conductive coating is 20 microns;
the conductive coating comprises the following substances in parts by mass: 98 parts of graphene material, 1 part of conductive agent and 1 part of binder;
the graphene is prepared by a physical method, an epitaxial growth method or an in-situ self-generated template method;
the thickness of the graphene material is 100 nanometers;
the specific surface area of the graphene material is 10 square meters per gram;
the area of the graphene material is 10 mu square meters;
the conductive agent is acetylene black; the binder comprises one or a combination of polyvinylidene fluoride, CMC, SBR and LA series binders;
the preparation method of the conductive coating comprises the following steps:
(a) Uniformly dispersing graphene, acetylene black, a binder and sodium dodecyl sulfate in a solvent to obtain mixed slurry;
(b) And spraying the mixed slurry on the inner wall of a steel shell, and then drying to obtain the graphene modified conductive coating.
2. An alkaline zinc-manganese cell comprising the steel can of claim 1.
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| KR20170114171A (en) * | 2016-04-05 | 2017-10-13 | 현대자동차주식회사 | Lithium Secondary Battery And Method of preparing |
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| CN106684390A (en) * | 2017-03-02 | 2017-05-17 | 中银（宁波）电池有限公司 | Battery current collector, preparation method thereof and alkaline zinc-manganese battery |
| CN107658477B (en) * | 2017-10-23 | 2020-03-17 | 四川长虹新能源科技股份有限公司 | Alkaline zinc-manganese dry battery positive steel shell and alkaline zinc-manganese dry battery |
| CN107834002A (en) * | 2017-11-22 | 2018-03-23 | 惠州市德赛电池有限公司 | A kind of battery modules being conveniently replaceable |
| CN109860515A (en) * | 2018-12-19 | 2019-06-07 | 苏州柔能纳米科技有限公司 | The preparation method of flexible alkaline primary battery anode |
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