CN104218228B - A kind of alkaline battery - Google Patents

A kind of alkaline battery Download PDF

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Publication number
CN104218228B
CN104218228B CN201410442719.0A CN201410442719A CN104218228B CN 104218228 B CN104218228 B CN 104218228B CN 201410442719 A CN201410442719 A CN 201410442719A CN 104218228 B CN104218228 B CN 104218228B
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China
Prior art keywords
graphene
battery
improve
negative pole
cell
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CN201410442719.0A
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CN104218228A (en
Inventor
唐录
徐燕玲
徐益军
谢红卫
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Zhongyin Ningbo Battery Co Ltd
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Zhongyin Ningbo Battery Co Ltd
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/362Composites
    • H01M4/364Composites as mixtures
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/24Alkaline accumulators
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/62Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624Electric conductive fillers
    • H01M4/625Carbon or graphite
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries

Abstract

Alkaline battery disclosed by the invention includes positive pole and negative pole, containing mass percent in positive pole and/or negative pole is the Graphene of 0.05 ~ 5%, use 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, it is also possible to reduce the consumption of positive conductive material, improve the content of cell active materials, thus improve discharge capacity of the cell and combination property, make battery have superior high-rate performance and superior small current performance concurrently;Graphene can improve mobility and the viscosity of negative pole as cathode additive agent, also can play certain electric action at battery discharge middle and late stage simultaneously, can improve the utilization rate of negative electrode active material.

Description

A kind of alkaline battery
Technical field
The present invention relates to a kind of battery, specifically a kind of alkaline battery.
Background technology
Alkaline battery generally includes box hat, anode ring, calamine cream, diaphragm tube, collector body, alkaline electrolyte, sealing ring etc..Number Code product and the development of electronic device digitizing technique, be unable to do without high power or the battery of pulsed discharge of heavy-current discharge, Traditional alkaline battery uses field major part to need the battery of small current superior performance, but alkaline battery technical field at present It is difficult to accomplish to have superior high-rate performance and superior small current performance concurrently.
Summary of the invention
The technical problem to be solved is to provide a kind of superior high-rate performance and superior small current performance of having concurrently Alkaline battery.
The present invention solves the technical scheme that above-mentioned technical problem used: a kind of alkaline battery, including positive pole and negative pole, described Positive pole and/or described negative pole in be the Graphene of 0.05~5% containing mass percent.
Use Graphene as the positive conductive agent of alkaline battery, be possible not only to effectively reduce the internal resistance of cell, improve positive electrode active material The utilization rate of matter, it is also possible to reduce the consumption of positive conductive material, improves the content of positive active material, thus improves battery and put Capacitance and combination property;Graphene can improve mobility and the viscosity of negative pole as cathode additive agent, simultaneously in battery discharge Later stage also can play certain electric action, can improve the utilization rate of negative electrode active material.
Preferably, the mass percent of described positive pole consists of: graphite 3~6%, Graphene 0.05~5%, potassium hydroxide are molten Liquid 1~3%, calcium stearate 0.05~0.5%, surplus is electrolytic manganese dioxide.Graphite and Graphene as the hybrid conductive agent of positive pole, It is possible not only to effectively reduce the internal resistance of cell, improves the utilization rate of active substance, it is also possible to reduce the consumption of positive conductive material, carry The content of high positive active material, thus improve discharge capacity of the cell.But when the content of positive conductive agent is too low, in battery Resistance increases, and can directly affect electrical property after the initial electrical performance of battery and high temperature storage;Too high levels when positive conductive agent Time, in battery, the content of positive active material can reduce relatively, thus affects battery small current performance.Therefore, in order to take into account The high-rate performance of battery and small current performance, make battery 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, simultaneously that potassium hydroxide is molten The content of liquid controls the content in 1~3%, calcium stearate and controls 0.05~0.5%, it is thus achieved that have the battery of relatively high discharge capacity.
Preferably, the concentration of the described potassium hydroxide solution in positive pole is 35~50%, both can ensure in positive pole production process Breading requirement, is unlikely to again to impact the electrical property of battery.
Additionally, by the content sum controlling graphite and Graphene be 3~7% or the ratio of content be 1:1~3, guaranteeing that battery is higher Discharge capacity on the basis of, can reduce hybrid conductive agent consumption further, improve cell active materials content, so that battery is put Capacitance improves further, and battery is not havinging the phenomenon that electrical property significantly declines after high temperature storage yet simultaneously.
Preferably, the mass percent of described negative pole consists of: Graphene 0.05~5%, polyacrylic acid 0~1.5%, polypropylene Acid sodium 0~1.5%, potassium hydroxide solution 30~45%, surplus is zinc powder.Form according to this mass percent, by Graphene, gather The calamine cream that acrylic acid, sodium polyacrylate and potassium hydroxide solution mix and blend are made is as battery cathode, to improving negative electrode active material The effect of matter utilization rate and discharge capacity of the cell is preferable, and can improve the combination property of battery.
Preferably, the concentration of the described potassium hydroxide solution in negative pole is 25~45%.
Compared with prior art, it is an advantage of the current invention that: alkaline battery disclosed by the invention, contain in its positive pole and/or negative pole The Graphene having mass percent to be 0.05~5%, uses Graphene as alkaline cell anode conductive agent, is possible not only to effectively drop The low internal resistance of cell, improves the utilization rate of active substance, it is also possible to reduce the consumption of positive conductive material, improves cell active materials Content, thus improve discharge capacity of the cell and combination property, make battery have superior high-rate performance and superior medium and small electricity concurrently Fluidity energy;Graphene can improve mobility and the viscosity of negative pole as cathode additive agent, also can rise at battery discharge middle and late stage simultaneously To certain electric action, the utilization rate of negative electrode active material can be improved.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is described in further detail.
The alkaline battery of embodiment 1~5, with the alkaline battery of comparative example 1~3 as a comparison, embodiment 1~5 and comparative example 1~3 The mass percent composition of positive pole be shown in Table 1, the mixing that the positive pole of the alkaline battery of embodiment 1~5 forms with Graphene and graphite Conductive agent is as positive conductive agent, and comparative example 1~3 is using graphite as positive conductive agent.Form respectively by the mass percent of table 1 Prepare embodiment 1~5 and the raw material of comparative example 1~3, and be fabricated to anode ring respectively, then be assembled into LR6 alkaline battery respectively, And in the environment of 20 ± 2 DEG C, test electrical property after initial electrical performance and high temperature storage, wherein initial electrical performance data are 20 ± 2 DEG C environment in place and test gained two days later, high temperature storage electrical property be 70 DEG C of environment are stored 7 days after, then at 20 ± 2 DEG C Environment in be incubated after one day and test gained.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 test Index and stopping potential are as follows: 24 Ω pulse 15s/min, 8h/d, stopping potential 1.0V;1h/d, cut-off electricity is put between 100mA Position 0.9V.For embodiment 1~5 and the alkaline battery of comparative example 1~3, every kind of discharge mode tests 9 batteries, its electrical property Test average result is shown in Table 2, and in table 2, test result is designated as 100% with the initial electrical performance of comparative example 1.
The alkaline battery of embodiment 6~8, with the alkaline battery of comparative example 4 as a comparison, embodiment 6~8 and comparative example 4 negative The mass percent composition of pole is shown in Table 3, with the addition of Graphene, in comparative example 4 not in the negative pole of the alkaline battery of embodiment 6~8 Adding Graphene, the mass percent composition of the negative pole of embodiment 6~8 and comparative example 4 is shown in Table 3.Mass percent by table 3 Composition prepares embodiment 6~8 and the raw material of comparative example 4 respectively.Respectively by the Graphene of embodiment 6~8, polyacrylic acid, poly-third The calamine cream that olefin(e) acid sodium and potassium hydroxide solution mix and blend are made is as battery cathode.The system of the negative pole of the alkaline battery of comparative example 4 Preparation Method is identical with embodiment 6~8, the difference is that only that comparative example 4 is not added with Graphene.By embodiment 6~8 and comparative example 4 Calamine cream be assembled into LR6 alkaline battery respectively, and in the environment of 20 ± 2 DEG C, test electricity after initial electrical performance and high temperature storage Performance, method of testing and condition and test index are identical with the alkaline battery of embodiment 1~5 with by current potential.For embodiment 6~8 and the alkaline battery of comparative example 4, every kind of discharge mode tests 9 batteries, and its electric performance test average result is shown in Table 4, table In 4, test result is designated as 100% with the initial electrical performance of comparative example 4.
Table 1 embodiment 1~5 and mass percent composition (%) of positive pole of comparative example 1~3
Graphene Graphite Calcium stearate Potassium hydroxide solution Electrolytic manganese dioxide
Comparative example 1 0 8 0.2 4 Surplus
Comparative example 2 0 6 0.2 4 Surplus
Comparative example 3 0 4 0.2 4 Surplus
Embodiment 1 2 6 0.2 4 Surplus
Embodiment 2 1.5 4.5 0.2 4 Surplus
Embodiment 3 1 3 0.2 4 Surplus
Embodiment 4 2 4 0.2 4 Surplus
Embodiment 5 3 3 0.2 4 Surplus
Table 2 embodiment 1~5 and the electric performance test average result of alkaline battery of comparative example 1~3
From table 2 it can be seen that use the hybrid conductive agent positive conductive agent as alkaline battery of Graphene and graphite composition, electricity The high-rate performance in pond, 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 3.6% Left and right.Visible alkaline battery of the present invention not only shows superior high-rate performance, shows superior small current performance 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 has declined, and when graphite usage amount is 4%, initial high-rate performance fall reaches about 18%, Especially after high temperature storage, high-rate performance fall is bigger, reaches about 50%.
Table 3 embodiment 6~8 and mass percent composition (%) of negative pole of comparative example 4
Graphene Polyacrylic acid Sodium polyacrylate Potassium hydroxide solution Zinc powder
Comparative example 4 0 0.35 0.35 33 Surplus
Embodiment 6 0.05 0.35 0.35 33 Surplus
Embodiment 7 1 0.35 0.35 33 Surplus
Embodiment 8 2 0.35 0.35 33 Surplus
Table 4 embodiment 6~8 and the electric performance test average result of alkaline battery of comparative example 4
From table 4, it can be seen that after adding Graphene in negative pole, the large, medium and small current capability of battery all increases, electricity greatly Fluidity the highest can promote 3.8%, the highest lifting of medium current performance 4.3%, the highest lifting of small area analysis performance 3.4%;And it is real The high-temperature shelf property executing example is better than control cell.

Claims (2)

1. an alkaline battery, including positive pole and negative pole, it is characterised in that in described negative pole containing mass percent be 0.05~the Graphene of 2%, the mass percent of described negative pole consists of: Graphene 0.05~2%, polyacrylic acid 0~1.5%, Sodium polyacrylate 0~1.5%, potassium hydroxide solution 30~45%, surplus is zinc powder.
Alkaline battery the most according to claim 1, it is characterised in that: the concentration of the described potassium hydroxide solution in negative pole It is 25~45%.
CN201410442719.0A 2014-09-02 2014-09-02 A kind of alkaline battery Active CN104218228B (en)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108550800B (en) * 2018-03-28 2020-11-10 深圳新源柔性科技有限公司 Composite electrode and battery

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101714632A (en) * 2009-11-26 2010-05-26 苏州大学 Mercury-free zinc alloy granules, preparation method thereof and alkali electrochemical battery
CN102792489A (en) * 2010-03-12 2012-11-21 吉列公司 Primary alkaline battery
CN103531757A (en) * 2012-07-04 2014-01-22 北京精密机电控制设备研究所 High-rate pulse discharge zinc-silver battery electrode composite material

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7045252B2 (en) * 2002-08-08 2006-05-16 The Gillette Company Alkaline battery including lambda-manganese dioxide
US7754386B2 (en) * 2005-11-28 2010-07-13 Pure Energy Visions Corporation Rechargeable alkaline manganese cell having reduced capacity fade and improved cycle life
CN101746755B (en) * 2009-12-14 2012-07-04 重庆大学 Method for preparing multi-layer graphene

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101714632A (en) * 2009-11-26 2010-05-26 苏州大学 Mercury-free zinc alloy granules, preparation method thereof and alkali electrochemical battery
CN102792489A (en) * 2010-03-12 2012-11-21 吉列公司 Primary alkaline battery
CN103531757A (en) * 2012-07-04 2014-01-22 北京精密机电控制设备研究所 High-rate pulse discharge zinc-silver battery electrode composite material

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