CN104218229B - A kind of alkaline cell anode and preparation method thereof - Google Patents
A kind of alkaline cell anode and preparation method thereof Download PDFInfo
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- CN104218229B CN104218229B CN201410443166.0A CN201410443166A CN104218229B CN 104218229 B CN104218229 B CN 104218229B CN 201410443166 A CN201410443166 A CN 201410443166A CN 104218229 B CN104218229 B CN 104218229B
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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
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/364—Composites as mixtures
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/24—Alkaline accumulators
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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
- 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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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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Abstract
Containing mass percent in alkaline cell anode disclosed by the invention is the Graphene of 0.05 ~ 5%, adopt Graphene as alkaline cell anode conductive agent, it is possible not only to effectively reduce the internal resistance of cell, improve the utilization rate of active substance, the consumption of positive conductive material can also be reduced, improve the content of cell active materials, thus improving discharge capacity of the cell and combination property；The preparation method of alkaline cell anode disclosed by the invention includes twice breading technique, Graphene is added at twice, and the addition of Graphene in second time breading process is controlled below 2%, make graphene dispersion uniformly and improve the utilization rate of positive active material, to guarantee the uniformity of second particle powder component and density, the anode ring weight making making is uniform.
Description
Technical field
The present invention relates to a kind of anode and preparation thereof, specifically a kind of alkaline cell anode and preparation method thereof.
Background technology
Alkaline battery generally includes box hat, anode ring, calamine cream, diaphragm tube, collector body, alkaline electrolyte, sealing ring etc..The development of digital product and electronic device digitizing technique, it be unable to do without the high power of heavy-current discharge or the battery of pulsed discharge, traditional alkaline battery uses field major part to need the battery of small current superior performance, but alkaline battery technical field is difficult to accomplish to have concurrently superior high-rate performance and superior small current performance at present, and the high-rate performance of battery or small current performance are closely related with the positive pole utilization rate of battery.
Summary of the invention
The technical problem to be solved is to provide a kind of alkaline cell anode and preparation method thereof, after this positive pole is assembled in alkaline battery, alkaline battery can be made to obtain superior high-rate performance and superior small current performance.
This invention address that the technical scheme that above-mentioned technical problem adopts is: a kind of alkaline cell anode, containing mass percent in this positive pole is the Graphene of 0.05～5%.
Adopt Graphene as the positive conductive agent of alkaline battery, it is possible not only to effectively reduce the internal resistance of cell, improves the utilization rate of positive active material, it is also possible to reduce the consumption of positive conductive material, improve the content of positive active material, thus improving discharge capacity of the cell and combination property.
Preferably, the mass percent of this positive pole consists of: graphite 3～6%, Graphene 0.05～5%, potassium hydroxide solution 1～3%, calcium stearate 0.05～0.5%, and surplus is electrolytic manganese dioxide.Graphite and Graphene, as the hybrid conductive agent of positive pole, being possible not only to effectively reduce the internal resistance of cell, improve the utilization rate of active substance, it is also possible to reduce the consumption of positive conductive material, improving the content of positive active material, thus improving discharge capacity of the cell.But when the content of positive conductive agent is too low, the internal resistance of cell increases, and electrical property after the initial electrical performance of battery and high temperature storage can be directly affected；When the too high levels of positive conductive agent, in battery, the content of positive active material can reduce relatively, thus affecting battery small current performance.Therefore, in order to take into account high-rate performance and the small current performance of battery, battery is made to have superior high-rate performance and superior small current performance concurrently, the content of graphite in positive pole is controlled the content in 3～6%, Graphene and controls 0.05～5% by the present invention, the content of potassium hydroxide solution is controlled the content in 1～3%, calcium stearate simultaneously and controls 0.05～0.5%, it is thus achieved that there is the battery of relatively high discharge capacity.
Preferably, the concentration of described potassium hydroxide solution is 35～50%, both can ensure the breading requirement in positive pole production process, is unlikely to again the electrical property of battery is impacted.
In addition, by control the content sum of graphite and Graphene be 3～7% or the ratio of content be 1:1～3, guaranteeing on the discharge capacity basis that battery is higher, hybrid conductive agent consumption can be reduced further, improve cell active materials content, so that discharge capacity of the cell improves further, simultaneously battery after high temperature storage without the phenomenon occurring that electrical property significantly declines.
The preparation method of a kind of alkaline cell anode, comprises the following steps:
1) raw material prepares: prepare electrolytic manganese dioxide, graphite, Graphene, calcium stearate and potassium hydroxide solution, carries out dispensing according to the mass percent that graphite 3～6%, Graphene 0.05～5%, potassium hydroxide solution 1～3%, calcium stearate 0.05～0.5%, surplus are electrolytic manganese dioxide；
2) first time breading: electrolytic manganese dioxide, graphite, calcium stearate and a part of Graphene mix and carry out dry stirring, adds potassium hydroxide solution afterwards and carries out wet stirring, after stirring through tabletting, pelletize, sieving obtains primary particle powder；
3) second time breading: the primary particle powder obtained is stirred, adds remaining Graphene while stirring, namely obtain second particle powder, described remaining Graphene weight/mass percentage composition≤2% in described positive pole after stirring；
4) anode ring is made: second particle powder is fabricated to anode ring, is described positive pole.
Preferably, step 1) in the content sum of the Graphene that adopts and graphite be 3～7%.
Preferably, step 1) in the ratio of the Graphene that adopts and content of graphite be 1:1～3.
Preferably, step 1) in the concentration of potassium hydroxide solution that adopts be 35～50%.
Preferably, step 1) in the electrolytic manganese dioxide that adopts be powdery, its particle diameter is less than 150 μm.Electrolytic manganese dioxide is as positive active material, by its size controlling below 150 μm, to guarantee its utilization rate.
The preparation method of alkaline cell anode disclosed by the invention, including twice breading technique, Graphene is added at twice, first time breading process first adds a part of Graphene, remaining Graphene adds in second time breading process, and the addition of Graphene in second time breading process is controlled below 2%, to guarantee the uniformity of second particle powder component and density, the anode ring weight making making is uniform.Graphene being added at twice, and while second time breading is stirred, adds the Graphene of less than 2%, be possible not only to make Graphene be disperseed uniformly, it is also possible to improving the conductivity of positive pole, thus improving the utilization rate of positive active material.Why adding remaining Graphene in second time breading, the frictional force being because in second time breading between particulate material is relatively big, can make the dispersion of Graphene evenly, thus the anode ring composition finally prepared, weight are uniform, and stable performance.
Compared with prior art, it is an advantage of the current invention that: containing mass percent in alkaline cell anode disclosed by the invention is the Graphene of 0.05～5%, adopt Graphene as alkaline cell anode conductive agent, it is possible not only to effectively reduce the internal resistance of cell, improve the utilization rate of active substance, the consumption of positive conductive material can also being reduced, improving the content of cell active materials, thus improving discharge capacity of the cell and combination property.The preparation method of alkaline cell anode disclosed by the invention, Graphene is not only made to be easily dispersed uniformly, also can improve the utilization rate of positive active material simultaneously, adopt the anode ring molding that the inventive method prepares good, hybrid conductive agent is uniformly dispersed, can make battery discharge uniformly, combination property improved.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is described in further detail.
The mass percent composition of the positive pole of embodiment 1～5 and comparative example 1～3 is in Table 1, and the hybrid conductive agent that embodiment 1～5 forms using Graphene and graphite is as conductive agent, and comparative example 1～3 is using graphite as conductive agent.The raw material preparing embodiment 1～5 and comparative example 1～3 respectively is formed by the mass percent of table 1, the preparation method of the positive pole of embodiment 1～5 is: electrolytic manganese dioxide, graphite, Graphene and calcium stearate is mixed and carries out dry stirring, add potassium hydroxide solution afterwards and carry out wet stirring, through tabletting, pelletize after stirring, sieving obtains granule powder, and this granule powder is fabricated to anode ring, it is the positive pole of embodiment 1～5.The preparation method of comparative example 1～3 is identical with embodiment 1～5, the difference is that only that comparative example 1～3 is not added with Graphene.The anode ring that embodiment 1～5 and comparative example 1～3 are made is assembled into LR6 alkaline battery respectively, and under the environment of 20 ± 2 DEG C, test electrical property after initial electrical performance and high temperature storage, wherein initial electrical performance data are place in the environment of 20 ± 2 DEG C to test gained two days later, high temperature storage electrical property is after storing 7 days in 70 DEG C of environment, then insulation tested gained after one day in the environment of 20 ± 2 DEG C.High-rate performance test index and as follows by current potential: 1000mA pulse 10s/m, 1h/d, stopping potential 0.9V；1500mW pulse (1500mW2s, 650mW28s) 10T/1h, 24h/d, stopping potential 1.05V.Medium current performance testing index and stopping potential are as follows: put 1h/d, stopping potential 0.9V between 250mA.Small area analysis performance testing index and stopping potential are as follows: 24 Ω pulse 15s/min, 8h/d, stopping potential 1.0V；1h/d, stopping potential 0.9V is put between 100mA.For the alkaline battery that embodiment 1～5 and comparative example 1～3 are made, every kind of discharge mode tests 9 batteries, and its electric performance test average result is in Table 2, and in table 2, test result is designated as 100% with the initial electrical performance of comparative example 1.
Embodiment 6～8 and comparative example 4, comparative example 5 the mass percent of positive pole form in Table 1, comparative example 4 is used alone the graphite of 5% as conductive agent, the hybrid conductive agent that embodiment 6～8 and comparative example 5 all form using Graphene and graphite is as conductive agent, the content of hybrid conductive agent is 5%, it is different in that the positive pole of embodiment 6～8 adopts the inventive method to prepare: add at twice by Graphene, first adding a part of Graphene in first time breading process, remaining Graphene adds in second time breading process.Comparative example 4, comparative example 5 preparation method and the embodiment 1～5 of positive pole identical.The anode ring that embodiment 6～8 and comparative example 4, comparative example 5 are made is assembled into LR6 alkaline battery respectively, the environment of 20 ± 2 DEG C is placed two days later, testing initial electrical performance under the environment of 20 ± 2 DEG C, method of testing is identical with the alkaline battery being made by embodiment 1～5 with by current potential with condition and test index.For the alkaline battery that embodiment 6～8 and comparative example 4, comparative example 5 are made, every kind of discharge mode tests 9 batteries, and its electric performance test average result is in Table 3, and in table 3, test result is designated as 100% with the initial electrical performance of comparative example 4.For the alkaline battery that embodiment 6～8 and comparative example 4, comparative example 5 are made, 9 batteries of every kind of discharge mode test, and calculating the evening ratio of every kind of discharge mode 9 batteries, result is in Table 4.
Mass percent composition (%) of the positive pole of table 1 embodiment 1～8 and comparative example 1～4
The electric performance test average result of the alkaline battery that table 2 embodiment 1～5 and comparative example 1～3 are made
From table 2 it can be seen that use the hybrid conductive agent positive conductive agent as alkaline battery of Graphene and graphite composition, the high-rate performance of battery, small current performance are obtained for raising, and significantly relaxation phenomenon does not occur in high temperature storage electrical property.The initial electrical performance of the alkaline battery of embodiment 2 improves maximum, and high-rate performance improves about 4.5%, and small current improves about 3.6%.Visible alkaline battery of the present invention not only high-rate performance is improved, and small current performance is also improved simultaneously.And comparative example 2 and comparative example 3, it is used alone graphite as positive conductive agent, although small current performance slightly improves, but high-rate performance but declines to some extent, and when graphite makes consumption be 4%, initial high-rate performance fall reaches about 18%, especially after high temperature storage, high-rate performance fall is bigger, reaches about 50%.
The electric performance test average result of the alkaline battery that table 3 embodiment 6～8 and comparative example 4, comparative example 5 are made
From table 3 it can be seen that when conductive agent consumption is 5%, after adding Graphene, the large, medium and small current capability of battery all increases, high-rate performance is the highest can promote about 10%, the highest lifting about 3.5% of medium current performance, the highest lifting about 2% of small area analysis performance.
The electric performance test evening ratio of the alkaline battery that table 4 embodiment 6～8 and comparative example 4, comparative example 5 are made
Comparative example 5 adds whole Graphene when a breading, does not add Graphene during secondary breading.From table 4, it can be seen that the initial electrical performance evening ratio of comparative example 5 is worst.And embodiment 6～8 is adopting this method, being added at twice by Graphene, be separately added into appropriate Graphene in twice breading technique, the initial electrical performance evening ratio of its battery made all relatively comparative example 5 is good.
Claims (5)
1. the preparation method of an alkaline cell anode, it is characterised in that comprise the following steps:
1) raw material prepares: prepare electrolytic manganese dioxide, graphite, Graphene, calcium stearate and potassium hydroxide solution, carries out dispensing according to the mass percent that graphite 3～6%, Graphene 0.05～5%, potassium hydroxide solution 1～3%, calcium stearate 0.05～0.5%, surplus are electrolytic manganese dioxide；
2) first time breading: electrolytic manganese dioxide, graphite, calcium stearate and a part of Graphene mix and carry out dry stirring, adds potassium hydroxide solution afterwards and carries out wet stirring, after stirring through tabletting, pelletize, sieving obtains primary particle powder；
3) second time breading: the primary particle powder obtained is stirred, adds remaining Graphene while stirring, namely obtain second particle powder, described remaining Graphene weight/mass percentage composition≤2% in described positive pole after stirring；
4) anode ring is made: second particle powder is fabricated to anode ring, is described positive pole.
2. preparation method according to claim 1, it is characterised in that step 1) in the concentration of potassium hydroxide solution that adopts be 35～50%.
3. preparation method according to claim 1 and 2, it is characterised in that step 1) in the content sum of the Graphene that adopts and graphite be 3～7%.
4. preparation method according to claim 1 and 2, it is characterised in that step 1) in the ratio of the Graphene that adopts and content of graphite be 1:1～3.
5. preparation method according to claim 1, it is characterised in that step 1) in the electrolytic manganese dioxide that adopts be powdery, its particle diameter is less than 150 μm.
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| CN108682784B (en) * | 2018-03-28 | 2020-08-14 | 连州市凌力电池配件有限公司 | Preparation process of primary alkaline battery anode |
| CN108615907B (en) * | 2018-03-28 | 2020-08-25 | 连州市凌力电池配件有限公司 | Preparation process of primary alkaline battery |
| CN111682189A (en) * | 2020-07-14 | 2020-09-18 | 无锡永华电池有限公司 | Anode material of alkaline battery |
| CN112582631A (en) * | 2020-12-14 | 2021-03-30 | 佛山市里昂贸易有限公司 | Dry battery electrode and preparation method thereof |
| CN112467157A (en) * | 2020-12-14 | 2021-03-09 | 佛山市里昂贸易有限公司 | Zinc-manganese dry battery and preparation method thereof |
| CN113964286A (en) * | 2021-10-20 | 2022-01-21 | 无锡永华电池有限公司 | Preparation device and preparation method of alkaline battery anode |
| CN116632247A (en) * | 2023-07-20 | 2023-08-22 | 珠海市冠力电池有限公司 | Lithium manganese button cell positive electrode material and preparation method and application thereof |
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| CN101714632B (en) * | 2009-11-26 | 2012-05-23 | 苏州大学 | Mercury-free zinc alloy granules, preparation method thereof and alkali electrochemical battery |
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