CN102376987A - Electrolyte of nickel hydrogen battery and nickel hydrogen battery - Google Patents
Electrolyte of nickel hydrogen battery and nickel hydrogen battery Download PDFInfo
- Publication number
- CN102376987A CN102376987A CN2010102602619A CN201010260261A CN102376987A CN 102376987 A CN102376987 A CN 102376987A CN 2010102602619 A CN2010102602619 A CN 2010102602619A CN 201010260261 A CN201010260261 A CN 201010260261A CN 102376987 A CN102376987 A CN 102376987A
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- Prior art keywords
- battery
- electrolyte
- nickel hydrogen
- concentration
- hydrogen battery
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000003792 electrolyte Substances 0.000 title claims abstract description 40
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title abstract description 27
- 229910052739 hydrogen Inorganic materials 0.000 title abstract description 13
- 239000001257 hydrogen Substances 0.000 title abstract description 13
- 229910052759 nickel Inorganic materials 0.000 title abstract description 13
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title abstract description 9
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims abstract description 19
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims abstract description 12
- 229910018095 Ni-MH Inorganic materials 0.000 claims description 31
- 229910018477 Ni—MH Inorganic materials 0.000 claims description 31
- 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 15
- 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 11
- 229910052708 sodium Inorganic materials 0.000 claims description 11
- 230000004888 barrier function Effects 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 4
- -1 hydroxyl ions Chemical class 0.000 abstract description 3
- 239000011149 active material Substances 0.000 abstract 1
- 238000000034 method Methods 0.000 description 12
- 239000007772 electrode material Substances 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 4
- 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
- 239000000203 mixture Substances 0.000 description 2
- 239000007773 negative electrode material Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 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
- 238000001035 drying Methods 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
- 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
Landscapes
- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
Abstract
The invention belongs to the field of nickel hydrogen batteries. To solve technical problems which comprise the limit improvement of the capacity of a nickel hydrogen battery and the short circuit of the nickel hydrogen battery and are caused by the dressing amount increase of active materials of electrodes, the invention provides an electrolyte of a nickel hydrogen battery, which comprises an alkali metal hydroxide and a soluble sulfide, wherein the concentration of hydroxyl ions provided by the alkali metal hydroxide is 5.0-9.0mol/L, and the concentration of the soluble sulfide is not more than 5mol/L. The IEC capacity of the nickel hydrogen battery with the electrolyte provided by the invention is improved by 2-6%, and safe problems of short circuit, electrolyte leakage and the like of the nickel hydrogen battery do not appear.
Description
Technical field
The invention belongs to the Ni-MH battery field, especially a kind of Ni-MH battery electrolyte and the Ni-MH battery that uses this electrolyte.
Background technology
Ni-MH battery is that a kind of capacity is high, charge-discharge performance is good, pollutes little chemical power source, all is widely used in fields such as electronics, communication, electric automobiles.Research coverage to Ni-MH battery is very wide, and wherein, improving battery capacity is an importance.At present, the method that improves the Ni-MH battery capacity comprises: improve battery preparation technique or structure, to increase electrode active material the dressing amount on the electrode current collecting body (promptly increasing the density of electrode active material on electrode current collecting body); Increase the positive active material quality, suitably reduce the negative electrode active material quality; Use the ball nickel and the alloy of high power capacity.Though above method can make battery capacity promote, and also has some problems: increase the dressing amount of electrode active material on electrode current collecting body and can increase electrode slice thickness, assembling back inside battery is consolidation more; The space reduces; Raising to capacity is limited, is unfavorable for that also electrolyte soaks into electrode slice, in addition; Barrier film is pierced through by electrode slice easily, forms internal short-circuit of battery.And increase the positive active material quality, suitably reduce the raising that the negative electrode active material quality is unfavorable for battery security.
Summary of the invention
To increase the Ni-MH battery capacity limited to the raising of Ni-MH battery capacity through increasing electrode active material dressing amount in order to solve; And cause the technical problem of battery short circuit easily; The present invention at first provides a kind of Ni-MH battery electrolyte, comprises alkali metal hydroxide, and 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.
To increase the Ni-MH battery capacity limited to the raising of Ni-MH battery capacity through increasing electrode active material dressing amount in order to solve; And cause the technical problem of battery short circuit easily; Comprise battery container, electrode group and electrolyte, electrode group and electrolyte are sealed in the battery container, and the electrode group comprises reels or stacked positive pole, barrier film and negative pole successively; Wherein, said 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 safety problems such as short circuit, leakage do not appear in battery.
Embodiment
To increase the Ni-MH battery capacity limited to the raising of Ni-MH battery capacity through increasing electrode active material dressing amount in order to solve; And cause the technical problem of battery short circuit easily; The present invention at first 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 does not have particular restriction, and NaOH (NaOH), potassium hydroxide (KOH), lithium hydroxide (LiOH) commonly used in the Ni-MH battery electrolyte all can be used for the present invention.The also not special restriction of the selection of dissolvable sulfide, for example 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 ionization goes out is oxidized to elemental sulfur, and elemental sulfur is grown in the anodal space, and when discharge, sulphur is reduced into sulphion, discharges electric charge.This process can improve battery capacity, but does not increase positive active material dressing amount.The inventor finds, when using vulcanized sodium, the effect of improving of battery capacity slightly is better than potassium sulfide, so 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.Vulcanized sodium concentration is crossed low not obvious to the raising of Ni-MH battery capacity, and the too high internal resistance of cell that then makes increases.When being 0.5～5.0mol/L, vulcanized sodium concentration can when improving battery capacity, its internal resistance be controlled in the reasonable range; When vulcanized sodium concentration is 3.2～3.5mol/L, battery capacity is improved with the effect of internal resistance control best, can make battery capacity nearly improve 6%, the increase of internal resistance simultaneously is no more than 7%.
Alkali metal hydroxide in the electrolyte preferably includes potassium hydroxide and lithium hydroxide, and the molar concentration rate of potassium hydroxide and lithium hydroxide is 6～7, and this helps improving the capability retention of 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 the battery container; The electrode group comprises reels or stacked positive pole, barrier film and negative pole successively, and wherein, electrolyte is the electrolyte that the specific embodiment of the invention provides.
The preparation of nickel-hydrogen battery electrode active material, conductive additive, collector body, barrier film or selection, the preparation method of battery etc. all belongs to the prior art in Ni-MH battery field, and little with inventive point relation of the present invention, so this repeats no more again.
Embodiment 1
1. electrolyte quota:
Get 15g potassium hydroxide, 1g lithium hydroxide, 10g vulcanized sodium, 40g water and add to stir in the beaker solid matter is dissolved fully, process 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 is made:
Covering in the cobalt ball nickel (Cologne, Henan) of 100g, add 1g conductive agent cobalt protoxide (Guangzhou Xing Litai), with 4g CMC (sodium carboxymethylcellulose) and 5g PTFE (polytetrafluoroethylene; Select PTFE as the battery binding agent) make binding agent, add 30g water and mix, be coated on the nickel foam after stirring; Dry; Compressing tablet is cut into slices, and gets the positive plate of 90mm * 42.0mm * 0.66mm;
3. the nickel-hydrogen battery negative pole sheet is made:
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 10g water and mix, be coated on the nickel plated steel strip after stirring, drying, compressing tablet is cut into slices, and gets the negative plate of 106mm * 42.0mm * 0.35mm.
4. making nickel hydrogen battery:
(battery is used polypropylene diaphragm according to positive plate, barrier film with the above positive plate that makes and negative plate; Be purchased), the order of negative plate stacks the back successively and reels, and injects the electrolyte that 2.1ml step 1 obtains, block; Seal and change into (the 0.1C charging that changes into 3 hours), get AA1500 finished product battery.
Comparative Examples 1
According to the method for embodiment 1, difference is: do not use electrolyte provided by the invention (being not contain dissolvable sulfide in the 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 Examples 2
According to the method for embodiment 2, difference is: do not contain dissolvable sulfide in the 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 Examples 3
According to the method for embodiment 3, difference is: do not contain dissolvable sulfide in the electrolyte.
The electrolyte prescription of table 1 embodiment
Performance test methods:
1.IEC capacity: the IEC volume test result of the Ni-MH battery of (with battery 0.1C charging 16 hours, 0.2C discharged into 1.0V, got the IEC capacity) embodiment and Comparative Examples sees table 2.
Table 2 Ni-MH battery IEC volume test result
Summary analysis 1 can be found out with table 2:
1. in electrolyte, add sulfide, can increase battery IEC capacity;
2. when dissolvable sulfide concentration was 3.2～3.5mol/L, battery capacity nearly improved 6%, and internal resistance simultaneously increases and is no more than 7%.The ratio dissolvable sulfide concentration that capacity improves is big when not selecting this most preferred range, and 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 the molar concentration rate of potassium hydroxide and lithium hydroxide is when being 5～7mol/L, and the battery capacity conservation rate is higher.The capacity of comprehensive relatively battery improves ratio, internal resistance and capability retention can be known, uses the Ni-MH battery combination property of above-mentioned electrolyte best.
Claims (6)
1. Ni-MH battery electrolyte; Comprise alkali metal hydroxide, the concentration of the hydroxide ion that said alkali metal hydroxide provides is 5.0～9.0mol/L, it is characterized in that; Also comprise dissolvable sulfide, the concentration of said dissolvable sulfide is no more than 5mol/L.
2. Ni-MH battery electrolyte as claimed in claim 1 is characterized in that, said dissolvable sulfide is a vulcanized sodium.
3. Ni-MH battery electrolyte as claimed in claim 2 is characterized in that, the concentration of vulcanized sodium is 0.5～5.0mol/L.
4. Ni-MH battery electrolyte as claimed in claim 3 is characterized in that, the concentration of vulcanized sodium is 3.2～3.5mol/L.
5. Ni-MH battery electrolyte as claimed in claim 4 is characterized in that said alkali metal hydroxide comprises potassium hydroxide and lithium hydroxide, and the molar concentration rate of potassium hydroxide and lithium hydroxide is 6～7.
6. Ni-MH battery; Comprise battery container, electrode group and electrolyte, electrode group and electrolyte are sealed in the battery container, and the electrode group comprises reels or stacked positive pole, barrier film and negative pole successively; It is characterized in that said electrolyte is any described electrolyte of claim 1～5.
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 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102376987A true CN102376987A (en) | 2012-03-14 |
| CN102376987B CN102376987B (en) | 2015-09-30 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201010260261.9A Withdrawn - After Issue CN102376987B (en) | 2010-08-19 | 2010-08-19 | A kind of Ni-MH battery electrolyte and Ni-MH battery |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102376987B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105144434A (en) * | 2013-02-06 | 2015-12-09 | 恩塞尔技术股份有限公司 | Battery comprising a coated iron anode and improved performance |
| CN108682901A (en) * | 2018-06-01 | 2018-10-19 | 河南省恒明新能源有限公司 | A kind of double pocket type Hawkins cells of large capacity |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1143839A (en) * | 1995-03-17 | 1997-02-26 | 佳能株式会社 | Electrodes for secondary cells, process for their production, and secondary cells having such electrodes |
| CN1739210A (en) * | 2003-01-20 | 2006-02-22 | 株式会社汤浅 | Closed nickel-hydrogen storage battery and its production method |
| WO2009108286A1 (en) * | 2008-02-28 | 2009-09-03 | Corning Incorporated | Electrochemical methods of making nanostructures |
-
2010
- 2010-08-19 CN CN201010260261.9A patent/CN102376987B/en not_active Withdrawn - After Issue
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1143839A (en) * | 1995-03-17 | 1997-02-26 | 佳能株式会社 | Electrodes for secondary cells, process for their production, and secondary cells having such electrodes |
| CN1739210A (en) * | 2003-01-20 | 2006-02-22 | 株式会社汤浅 | Closed nickel-hydrogen storage battery and its production method |
| WO2009108286A1 (en) * | 2008-02-28 | 2009-09-03 | Corning Incorporated | Electrochemical methods of making nanostructures |
Non-Patent Citations (2)
| Title |
|---|
| P. PERIASAMY, B. RAMESH BAHU, S. VENKATAKRISHNA IYER: "Performance characterization of sintered iron electrodes in nickel/iron alkaline batteries", 《JOURNAL OF POWER SOURCES》 * |
| WEN-HUA ZHU,JIA-JUN KE,HONG-MEI YU,DENG-JUN ZHANG: "A study of the electrochemistry of nickel hydroxide electrodes with various additives", 《JOURNAL OF POWER SOURCES》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105144434A (en) * | 2013-02-06 | 2015-12-09 | 恩塞尔技术股份有限公司 | Battery comprising a coated iron anode and improved performance |
| 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 |
| CN109192976A (en) * | 2013-02-06 | 2019-01-11 | 恩塞尔技术股份有限公司 | The battery of iron anode comprising coating and improved performance |
| CN109192976B (en) * | 2013-02-06 | 2021-08-03 | 恩塞尔技术股份有限公司 | Battery comprising coated iron anode and improved performance |
| CN108682901A (en) * | 2018-06-01 | 2018-10-19 | 河南省恒明新能源有限公司 | A kind of double pocket type Hawkins cells of large capacity |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102376987B (en) | 2015-09-30 |
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