CN102376987B - A kind of Ni-MH battery electrolyte and Ni-MH battery - Google Patents
A kind of Ni-MH battery electrolyte and Ni-MH battery Download PDFInfo
- Publication number
- CN102376987B CN102376987B CN201010260261.9A CN201010260261A CN102376987B CN 102376987 B CN102376987 B CN 102376987B CN 201010260261 A CN201010260261 A CN 201010260261A CN 102376987 B CN102376987 B CN 102376987B
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- Prior art keywords
- battery
- electrolyte
- concentration
- hydroxide
- capacity
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- 229910018095 Ni-MH Inorganic materials 0.000 title claims abstract description 34
- 229910018477 Ni—MH Inorganic materials 0.000 title claims abstract description 34
- 239000003792 electrolyte Substances 0.000 title claims abstract description 34
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims abstract description 18
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims abstract description 5
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 29
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 28
- 239000011734 sodium Substances 0.000 claims description 14
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 10
- 229910052708 sodium Inorganic materials 0.000 claims description 10
- 230000004888 barrier function Effects 0.000 claims description 6
- 238000004804 winding Methods 0.000 claims description 4
- 239000007772 electrode material Substances 0.000 abstract description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 11
- 238000000034 method Methods 0.000 description 11
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052759 nickel Inorganic materials 0.000 description 5
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 239000007774 positive electrode material Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 2
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 239000007773 negative electrode material Substances 0.000 description 2
- -1 polytetrafluoroethylene Polymers 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000001996 bearing alloy Substances 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 239000002482 conductive additive Substances 0.000 description 1
- 238000007596 consolidation process Methods 0.000 description 1
- FANSKVBLGRZAQA-UHFFFAOYSA-M dipotassium;sulfanide Chemical compound [SH-].[K+].[K+] FANSKVBLGRZAQA-UHFFFAOYSA-M 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- DPLVEEXVKBWGHE-UHFFFAOYSA-N potassium sulfide Chemical compound [S-2].[K+].[K+] DPLVEEXVKBWGHE-UHFFFAOYSA-N 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
-
- 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
Abstract
The invention belongs to Ni-MH battery field.In order to solve by increasing electrode active material dressing amount, to increase the raising of Ni-MH battery capacity to Ni-MH battery capacity limited, and easily cause the technical problem of battery short circuit, first the present invention provides a kind of Ni-MH battery electrolyte, comprise alkali metal hydroxide, the concentration of the hydroxide ion that alkali metal hydroxide provides is 5.0 ~ 9.0mol/L, also comprise dissolvable sulfide, the concentration of dissolvable sulfide is no more than 5mol/L.Use the IEC capacity of the Ni-MH battery of electrolyte provided by the invention to improve 2% ~ 6%, and there is not the safety problem such as short circuit, leakage in battery.
Description
Technical field
The invention belongs to Ni-MH battery field, the Ni-MH battery of especially a kind of Ni-MH battery electrolyte and this electrolyte of use.
Background technology
Ni-MH battery is that a kind of capacity is high, charge-discharge performance good, pollutes little chemical power source, is all widely used in fields such as electronics, communication, electric automobiles.Research coverage for Ni-MH battery is very wide, and wherein, improving battery capacity is an importance.At present, the method improving Ni-MH battery capacity comprises: improve battery preparation technique or structure, to increase the dressing amount of electrode active material on electrode current collecting body (namely increasing the density of electrode active material on electrode current collecting body); Increase positive active material quality, suitably reduce negative electrode active material quality; Use ball nickel and the alloy of high power capacity.Although above method can make battery capacity promote, but also there are some problems: increase the dressing amount of electrode active material on electrode current collecting body and can increase electrode slice thickness, inside battery consolidation more after assembling, space reduces, limited to the raising of capacity, be also unfavorable for that electrolyte infiltrates electrode slice, in addition, barrier film is easily pierced through by electrode slice, forms internal short-circuit of battery.And increase positive active material quality, suitably reduce the raising that negative electrode active material quality is unfavorable for battery security.
Summary of the invention
In order to solve by increasing electrode active material dressing amount, to increase the raising of Ni-MH battery capacity to Ni-MH battery capacity limited, and easily cause the technical problem of battery short circuit, first the present invention provides a kind of Ni-MH battery electrolyte, comprise alkali metal hydroxide, the concentration of the hydroxide ion that alkali metal hydroxide provides is 5.0 ~ 9.0mol/L, also comprise dissolvable sulfide, the concentration of dissolvable sulfide is no more than 5mol/L.
In order to solve by increasing electrode active material dressing amount, to increase the raising of Ni-MH battery capacity to Ni-MH battery capacity limited, and easily cause the technical problem of battery short circuit, comprise battery container, electrode group and electrolyte, electrode group and electrolyte are sealed in battery container, electrode group comprises winding or stacked positive pole, barrier film and negative pole successively, wherein, described electrolyte is electrolyte provided by the invention.
Adopt the IEC capacity of the Ni-MH battery of electrolyte provided by the invention to improve 2% ~ 6%, and there is not the safety problem such as short circuit, leakage in battery.
Embodiment
In order to solve by increasing electrode active material dressing amount, to increase the raising of Ni-MH battery capacity to Ni-MH battery capacity limited, and easily cause the technical problem of battery short circuit, first the present invention provides a kind of Ni-MH battery electrolyte, comprise alkali metal hydroxide and dissolvable sulfide, the concentration of the hydroxide ion that alkali metal hydroxide provides is 5.0 ~ 9.0mol/L, and the concentration of dissolvable sulfide is no more than 5mol/L.The selection of alkali metal hydroxide is not particularly limited, and NaOH (NaOH) conventional in Ni-MH battery electrolyte, potassium hydroxide (KOH), lithium hydroxide (LiOH) all can be used for the present invention.The selection of dissolvable sulfide is also not particularly limited, such as vulcanized sodium (Na
2s), potassium sulfide (K
2s), all can be used for the present invention.In battery charging process, the sulphion that dissolvable sulfide ionizes out is oxidized to elemental sulfur, and elemental sulfur growth is in the space of positive pole, and when discharging, sulphur is reduced into sulphion, release electric charge.This process can improve battery capacity, but does not increase positive active material dressing amount.Inventor finds, when using vulcanized sodium, is slightly better than potassium sulfide to the improvement effect of battery capacity, therefore the preferred vulcanized sodium of dissolvable sulfide.
The concentration of vulcanized sodium is preferably 0.5 ~ 5.0mol/L, more preferably 3.2 ~ 3.5mol/L.The too low raising to Ni-MH battery capacity of vulcanized sodium concentration is not obvious, too high, and the internal resistance of cell is increased.Can while raising battery capacity, its internal resistance be controlled in rational scope when vulcanized sodium concentration is 0.5 ~ 5.0mol/L; When vulcanized sodium concentration is 3.2 ~ 3.5mol/L, best to the effect that battery capacity improves and internal resistance controls, battery capacity can be made to improve 6% nearly, and internal resistance simultaneously increases and is no more than 7%.
Alkali metal hydroxide in electrolyte preferably includes potassium hydroxide and lithium hydroxide, and the molar concentration rate of potassium hydroxide and lithium hydroxide is 6 ~ 7, and this is conducive to the capability retention improving battery.
The specific embodiment of the invention also provides a kind of Ni-MH battery, comprise battery container, electrode group and electrolyte, electrode group and electrolyte are sealed in battery container, electrode group comprises winding or stacked positive pole, barrier film and negative pole successively, wherein, the electrolyte that provides for the specific embodiment of the invention of electrolyte.
The preparation of nickel-hydrogen battery electrode active material, conductive additive, collector body, barrier film or selection, the preparation method of battery etc. all belong to the prior art in Ni-MH battery field, and little with inventive point relation of the present invention, therefore this repeats no more again.
Embodiment 1
1. electrolyte quota:
Get 15g potassium hydroxide, 1g lithium hydroxide, 10g vulcanized sodium, 40g water add in beaker to stir that solid matter is dissolved completely, make Ni-MH battery electrolyte.KOH, LiOH, Na
2the concentration of S is respectively: 6.75mol/L, 1.0mol/L, 3.25mol/L.
2. positive plate for nickel-hydrogen cell makes:
Cover in cobalt ball nickel (Cologne, Henan) at 100g, add 1g conductive agent cobalt protoxide (Guangzhou Xing Litai), with 4g CMC (sodium carboxymethylcellulose) and 5g PTFE (polytetrafluoroethylene, select the PTFE being used as battery binding agent) make binding agent, add the mixing of 30g water, be coated on after stirring in nickel foam, dry, compressing tablet, section, obtains the positive plate of 90mm × 42.0mm × 0.66mm;
3. nickel-hydrogen battery negative pole sheet makes:
In the hydrogen bearing alloy of 100g, add 1g conductive agent nickel powder (Jinchuan production), make binding agent with 4g CMC and 5g PTFE, add the mixing of 10g water, be coated on after stirring on nickel plated steel strip, dry, compressing tablet, section, obtains the negative plate of 106mm × 42.0mm × 0.35mm.
4. making nickel hydrogen battery:
By positive plate obtained above and negative plate according to positive plate, barrier film (battery polypropylene diaphragm, be purchased), the order of negative plate stacks rear winding successively, inject the electrolyte that 2.1ml step 1 obtains, block, sealing changes into (0.1C changed into charges 3 hours), obtains AA1500 resultant battery.
Comparative example 1
According to the method for embodiment 1, difference is: do not use electrolyte provided by the invention (namely not containing dissolvable sulfide in electrolyte).
Embodiment 2
According to the method for embodiment 1, difference is: KOH, LiOH, Na
2the concentration of S is respectively: 7.25mol/L, 1.5mol/L, 3.0mol/L.
Comparative example 2
According to the method for embodiment 2, difference is: not containing dissolvable sulfide in electrolyte.
Embodiment 3
According to the method for embodiment 1, difference is: KOH, LiOH, Na
2the concentration of S is respectively: 6.0mol/L, 1.0mol/L, 3.25mol/L.
Comparative example 3
According to the method for embodiment 3, difference is: not containing dissolvable sulfide in electrolyte.
The electrolyte prescription of table 1 embodiment
Performance test methods:
1.IEC capacity: the IEC volume test of the Ni-MH battery of (charged by battery 0.1C 16 hours, 0.2C discharges into 1.0V, obtains IEC capacity) embodiment and comparative example the results are shown in Table 2.
Table 2 Ni-MH battery IEC volume test result
Summary analysis 1 and table 2 can be found out:
1. add sulfide in the electrolytic solution, battery IEC capacity can be increased;
2. when dissolvable sulfide concentration is 3.2 ~ 3.5mol/L, battery capacity improves 6% nearly, and internal resistance simultaneously increases and is no more than 7%.Large when the ratio dissolvable sulfide concentration that capacity improves does not select this most preferred range, internal resistance simultaneously increases less.
3. dissolvable sulfide concentration is 3.2 ~ 3.5mol/L, and the concentration of the hydroxide ion that alkali metal hydroxide provides is 5.0 ~ 9.0mol/L, and when the molar concentration rate of potassium hydroxide and lithium hydroxide is 5 ~ 7mol/L, battery capacity conservation rate is higher.It is known that the capacity of Integrated comparative battery improves ratio, internal resistance and capability retention, uses the Ni-MH battery combination property of above-mentioned electrolyte best.
Claims (2)
1. a Ni-MH battery electrolyte, comprise alkali metal hydroxide, the concentration of the hydroxide ion that described alkali metal hydroxide provides is 5.0 ~ 9.0mol/L, it is characterized in that, also comprise dissolvable sulfide, described dissolvable sulfide is vulcanized sodium, and the concentration of described vulcanized sodium is 3.2 ~ 3.5mol/L; Described alkali metal hydroxide comprises potassium hydroxide and lithium hydroxide, and the molar concentration rate of potassium hydroxide and lithium hydroxide is 6 ~ 7.
2. a Ni-MH battery, comprise battery container, electrode group and electrolyte, electrode group and electrolyte are sealed in battery container, and electrode group comprises winding or stacked positive pole, barrier film and negative pole successively, it is characterized in that, described electrolyte is electrolyte according to claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010260261.9A CN102376987B (en) | 2010-08-19 | 2010-08-19 | A kind of Ni-MH battery electrolyte and Ni-MH battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010260261.9A CN102376987B (en) | 2010-08-19 | 2010-08-19 | A kind of Ni-MH battery electrolyte and Ni-MH battery |
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| Publication Number | Publication Date |
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| CN102376987A CN102376987A (en) | 2012-03-14 |
| CN102376987B true CN102376987B (en) | 2015-09-30 |
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| CN201010260261.9A Withdrawn - After Issue CN102376987B (en) | 2010-08-19 | 2010-08-19 | A kind of Ni-MH battery electrolyte and Ni-MH battery |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105144434B (en) * | 2013-02-06 | 2018-09-07 | 恩塞尔技术股份有限公司 | Including the iron anode of coating and the accumulator of improved performance |
| CN108682901B (en) * | 2018-06-01 | 2020-05-19 | 河南省恒明新能源有限公司 | High-capacity double-bag type iron-nickel battery |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1739210A (en) * | 2003-01-20 | 2006-02-22 | 株式会社汤浅 | Closed nickel-hydrogen storage battery and its production method |
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| JP3387724B2 (en) * | 1995-03-17 | 2003-03-17 | キヤノン株式会社 | Electrode for secondary battery, method of manufacturing the same, and secondary battery having the electrode |
| WO2009108286A1 (en) * | 2008-02-28 | 2009-09-03 | Corning Incorporated | Electrochemical methods of making nanostructures |
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- 2010-08-19 CN CN201010260261.9A patent/CN102376987B/en not_active Withdrawn - After Issue
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1739210A (en) * | 2003-01-20 | 2006-02-22 | 株式会社汤浅 | Closed nickel-hydrogen storage battery and its production method |
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| CN102376987A (en) | 2012-03-14 |
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Effective date of registration: 20201126 Address after: 214500 No. 8, East Road, Liuguanggang, Chengnan Park, Jingjiang Economic Development Zone, Taizhou City, Jiangsu Province Patentee after: JINGJIANG HONGTAI TOYS Co.,Ltd. Address before: BYD 518118 Shenzhen Road, Guangdong province Pingshan New District No. 3009 Patentee before: BYD Co.,Ltd. |
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Address after: No. 22, Deyu Road, Jingjiang City, Taizhou City, Jiangsu Province, 214500 Patentee after: Jingjiang Hongtai Toys Co.,Ltd. Address before: Building 2, No. 8, Liuweigang East Road, Chengnan Park, Jingjiang Economic Development Zone, Taizhou City, Jiangsu Province, 214500 Patentee before: JINGJIANG HONGTAI TOYS Co.,Ltd. |
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Effective date of registration: 20220908 Address after: No. 99, Suyuan Thermal Circuit, Jingjiang City, Taizhou City, Jiangsu Province, 214500 Patentee after: Jiangsu Yangxian Technology Co.,Ltd. Address before: No. 22, Deyu Road, Jingjiang City, Taizhou City, Jiangsu Province, 214500 Patentee before: Jingjiang Hongtai Toys Co.,Ltd. |
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