CN101227003A - Lithium cell including organic solvent electrolytic solution - Google Patents
Lithium cell including organic solvent electrolytic solution Download PDFInfo
- Publication number
- CN101227003A CN101227003A CNA2008100262244A CN200810026224A CN101227003A CN 101227003 A CN101227003 A CN 101227003A CN A2008100262244 A CNA2008100262244 A CN A2008100262244A CN 200810026224 A CN200810026224 A CN 200810026224A CN 101227003 A CN101227003 A CN 101227003A
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- CN
- China
- Prior art keywords
- organic solvent
- lithium
- battery
- electrolytic solution
- iodine
- 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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- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 44
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 239000003960 organic solvent Substances 0.000 title claims abstract description 42
- 239000008151 electrolyte solution Substances 0.000 title claims description 19
- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Chemical compound [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 claims abstract description 38
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052740 iodine Inorganic materials 0.000 claims abstract description 17
- 239000011630 iodine Substances 0.000 claims abstract description 17
- 239000003792 electrolyte Substances 0.000 claims abstract description 15
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 claims abstract description 14
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000000203 mixture Substances 0.000 claims abstract description 7
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000012528 membrane Substances 0.000 claims abstract description 5
- 229910052751 metal Inorganic materials 0.000 claims abstract description 5
- 239000002184 metal Substances 0.000 claims abstract description 5
- 239000011149 active material Substances 0.000 claims abstract description 3
- NIFIFKQPDTWWGU-UHFFFAOYSA-N pyrite Chemical compound [Fe+2].[S-][S-] NIFIFKQPDTWWGU-UHFFFAOYSA-N 0.000 claims description 15
- 238000002360 preparation method Methods 0.000 claims description 13
- 229910052683 pyrite Inorganic materials 0.000 claims description 12
- 239000011028 pyrite Substances 0.000 claims description 12
- 239000003791 organic solvent mixture Substances 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 229940095991 ferrous disulfide Drugs 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 239000007774 positive electrode material Substances 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- 239000005030 aluminium foil Substances 0.000 claims description 5
- 239000011230 binding agent Substances 0.000 claims description 5
- 239000006229 carbon black Substances 0.000 claims description 5
- 239000002482 conductive additive Substances 0.000 claims description 5
- 239000010439 graphite Substances 0.000 claims description 5
- 229910002804 graphite Inorganic materials 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 5
- 239000002002 slurry Substances 0.000 claims description 5
- 229910000838 Al alloy Inorganic materials 0.000 claims description 4
- YFXWODPYUNGUEE-UHFFFAOYSA-N [I].[Li] Chemical compound [I].[Li] YFXWODPYUNGUEE-UHFFFAOYSA-N 0.000 claims description 4
- JFBZPFYRPYOZCQ-UHFFFAOYSA-N [Li].[Al] Chemical compound [Li].[Al] JFBZPFYRPYOZCQ-UHFFFAOYSA-N 0.000 claims description 4
- 238000003487 electrochemical reaction Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 239000012429 reaction media Substances 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- 230000000694 effects Effects 0.000 claims description 3
- 238000002347 injection Methods 0.000 claims description 3
- 239000007924 injection Substances 0.000 claims description 3
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims 1
- 238000010438 heat treatment Methods 0.000 claims 1
- 238000012856 packing Methods 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 229910000339 iron disulfide Inorganic materials 0.000 abstract description 4
- 239000005486 organic electrolyte Substances 0.000 abstract description 3
- 238000005192 partition Methods 0.000 abstract 2
- 229910000831 Steel Inorganic materials 0.000 abstract 1
- NFMAZVUSKIJEIH-UHFFFAOYSA-N bis(sulfanylidene)iron Chemical compound S=[Fe]=S NFMAZVUSKIJEIH-UHFFFAOYSA-N 0.000 abstract 1
- 239000010959 steel Substances 0.000 abstract 1
- 238000005516 engineering process Methods 0.000 description 8
- 239000011572 manganese Substances 0.000 description 6
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 4
- 229910052748 manganese Inorganic materials 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 238000004804 winding Methods 0.000 description 2
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 239000002699 waste material 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
- Primary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention relates to a lithium battery which contains an organic solvent electrolyte with iodine, which belongs to the field of batteries, in particular to a lithium battery of an organic electrolyte, the lithium battery which contains the organic solvent electrolyte with the iodine comprises a shell, an electrolyte, a positive plate and a negative plate, wherein the positive plate is a pole plate which is coated with an iron disulfide active material, a porous partition membrane which plays the role of separating the positive and the negative electrodes is inserted between a metal lithium ribbon and the positive plate, and the porous partition membrane is winded into a battery cell to put into a steel shell, after organic solvent with iodine is injected, and the lithium battery is sealed. The organic solvent electrolyte comprises dimethyl ethane and dioxolane which are dissolved with the iodine, and is also capable of being obtained from the mixture of the dimethyl ethane and dioxolane. The lithium battery of the invention has simple production process and high yield, production problem of an organic solvent electrolyte of lithium iodide is solved, and the producing cost of the battery is reduced.
Description
Technical field
The lithium battery that the present invention contains organic solvent electrolytic solution belongs to field of batteries, particularly relates to a kind of lithium battery of organic electrolyte.
Background technology
Along with the development of electronic technology and information technology, also require the performance of battery various aspects to be greatly developed, particularly more and more higher to the requirement high and power density of the energy density of battery.And common alkaline Mn cell is in this development trend process, and the shortcoming of its distinctive large current discharging capability difference shows more and more obviously.With the digital camera is example, and the operating time of conventional base manganese cell is very short, and most of capacity is not emitted, so in used these specific occasions, the conventional base manganese cell was inappropriate or perhaps very waste.Patent 200480034479.5 discloses a kind of lithium/iron disulfide manufacturing technology of high discharge capacity, improves greatly than its discharge capacity under big electric current with the conventional base manganese cell.Alkaline Mn cell in the 1A discharge capacity only less than the 300mAh Capacity Ratio, and lithium/iron disulfide system discharge capacity under the 1A discharging current can reach 3000mAh, so lithium/pyrite battery is compared with the conventional base manganese cell and had very large advantage.In the lithium/pyrite battery system, usually technology is to adopt lithium iodide electrolyte to be used as lithium ion to move to anodal media from negative pole, need anhydrous lithium iodide salt in the lithium iodide electrolyte quota process, the preparation of anhydrous lithium iodide is very a difficulty and a very expensive process.Lithium iodide can be removed the most crystallization water about 150 ℃ in dry run, but even remaining crystallization water is not easy to remove under the situation that significantly improves temperature, this is because lithium iodide is being higher than under 150 ℃ and can decomposing.For suppress lithium iodide at high temperature decomposition and prepare anhydrous lithium iodide, common technology is that gas such as logical HI suppresses to decompose when lithium iodide is dry.Thereby the anhydrous lithium iodide process complexity that obtains by this technology, shortcoming such as yield poorly, cost an arm and a leg.
Summary of the invention
The objective of the invention is to avoid weak point of the prior art, and a kind of electrolyte of independent preparation anhydrous lithium iodide salt as lithium/pyrite battery that need not to adopt is provided, utilize to contain the lithium battery of organic solvent as the electrolyte of lithium/pyrite battery.
The purpose of this invention is to provide a kind of lithium battery preparation method who contains organic solvent electrolytic solution.
The objective of the invention is to realize by following measure: the lithium battery that contains organic solvent electrolytic solution is made up of housing, electrolyte, positive plate and negative plate, adopt the made positive plate of positive active material, adopt the made negative plate of negative electrode active material, insert porous insulating film between positive plate and the negative plate, contain organic solvent electrolytic solution through putting into housing behind the coiling, in housing, charging into.
Positive plate is the anodal powder of ferrous disulfide, binding agent, conductive additive, and carbon black and graphite, organic solvent stir after mixing mutually, and scattered positive active material slurry is coated on the aluminium foil, roll and are cut into suitable dimensions.
Negative plate is metal lithium bands or lithium-aluminium alloy band.
Electrolyte adopts and contains the electrochemical reaction media of the organic solvent mixture of iodine as lithium/pyrite battery, and organic solvent comprises dimethyl ethane (DME), dioxolane (DIO), also can be both mixtures.Add iodine in organic solvent, the concentration of iodine in organic solvent is 0.1mol/l～1.5mol/l.
After containing the organic solvent mixture adding lithium/pyrite battery of iodine, the reaction that iodine and lithium at first take place is generated lithium iodide, the reaction potential of iodine lithium is higher than the reaction potential (greater than 500mV) of lithium/iron disulfide, therefore can be on the normal working voltage scope of lithium/pyrite battery, generate lithium iodide safely and do not relate to the electrochemical reducting reaction of ferrous disulfide, and the lithium iodide that generates is dissolved in the organic electrolyte that is further used as lithium/pyrite battery in the organic solvent.
The reaction of iodine lithium is at room temperature slow, can quicken by suitable mode.Concerning injecting the containing the organic mixture of iodine of lithium/pyrite battery, can simply quicken by the mode that heats, temperature range is between 45 ℃～85 ℃; The formation speed of lithium iodide is accelerated, and current range is between 0.001C ~ 0.5C.
The present invention contains the lithium battery preparation method of organic solvent electrolytic solution, negative plate is lithium metal or lithium-aluminium alloy band, positive plate is to apply ferrous disulfide active material pole piece, in the middle of negative plate and positive plate, insert and play the porous isolating membrane that separates the both positive and negative polarity effect, be wound into electric core, the electric core of winding is put into box hat, seals after injection contains the organic solvent mixture.
Contain the electrochemical reaction media of the organic solvent mixture of iodine as lithium/pyrite battery, organic solvent comprises dimethyl ethane (DME), dioxolane (DIO), also can be the mixture of their both any ratios.
Add iodine in organic solvent, the concentration of iodine in organic solvent is 0.1mol/l～1.5mol/l.
Positive plate is the anodal powder of ferrous disulfide, binding agent Kynoar (PVDF761), conductive additive carbon black and graphite, organic solvent N, N-dimethyl pyrrolidone (NMP), stir after mixing mutually, scattered positive active material slurry is coated on the aluminium foil, rolls and be cut into the positive plate that suitable dimensions is battery.Positive plate by dry and remove wherein moisture fully after, put into relative humidity and be lower than under 3% the environment.
Lithium battery production process of the present invention is simplified, and the output height has solved the production problem of lithium iodide organic electrolytic solution, has reduced the production cost of battery.
Embodiment
The present invention is further described below in conjunction with embodiment.
Embodiment 1
Contain the preparation of organic solvent mixture: get anhydrous dioxolane DIO500ml, anhydrous dimethyl base ethane DME500ml, be configured to 1: 1 mixed solvent of volume ratio, take by weighing purity and be 99.9% iodine 126.9g, be dissolved in the mixed solvent, be configured to contain the organic solvent mixture of iodine 1mol/l.
The preparation of lithium/pyrite battery: at first be the anodal powder weight ratio 91% of weighing ferrous disulfide, binding agent Kynoar (PVDF761) weight ratio 3.5%, conductive additive carbon black weight ratio 2.5% and graphite weight ratio 3%, add organic solvent N, N-dimethyl pyrrolidone (NMP) is stirred to evenly, scattered positive active material slurry is coated on the aluminium foil, rolls the positive plate that is cut into battery.After positive plate passes through the dry moisture of also removing fully wherein, putting into relative humidity is lower than under 3% the environment, in the middle of metal lithium bands and positive plate, insert and play the porous isolating membrane that separates the both positive and negative polarity effect, be wound into columned electric core, the electric core of winding is put into box hat, seals after injection contains organic solvent mixture 1.8g.
Embodiment 2
High temperature accelerated reaction method: the battery that assembles according to embodiment 1 shelved for 1 week under 65 ℃ of high temperature after, battery take out at room temperature leave standstill 1 day after, battery is carried out stopping discharge behind the 1A pre-arcing 6min.After shelving 30 days, battery is carried out 2A be discharged to 1.0V.
Embodiment 3
Little electric current forced electric discharge method: after leaving standstill 1 day under the battery room temperature that assembles according to embodiment 1,10ma stops discharge after being discharged to the voltage 1.6V of battery, at room temperature leave standstill 2 days after, battery is carried out stopping discharge behind the 1A pre-arcing 6min.After shelving 30 days, battery is carried out 2A be discharged to 1.0V.
Comparative example 1
Usually lithium iodide electrolyte battery preparation under the technology: except what inject is not to contain the organic mixture of iodine, but commodity 1mol/l lithium iodide electrolyte 1.8g, other process such as embodiment 1.After the battery that assembles is at room temperature shelved 3 days, battery is carried out stopping discharge behind the 1A pre-arcing 6min.After shelving 30 days, battery is carried out 2A be discharged to 1.0V.
The performance of the various batteries of table 1 relatively
| Embodiment 2 | Embodiment 3 | Comparative example 1 | |
| Shelve the internal resistance of cell after 30 days | 106 milliohms | 110 milliohms | 109 milliohms |
| Shelve battery 2A discharge capacity after 30 days | 2143mah | 2068mah | 2110mah |
| Shelve after 30 days the battery 2A preceding ten minutes minimum voltages that discharge | 1.243V | 1.233V | 1.239V |
Claims (8)
1. a lithium battery that contains organic solvent electrolytic solution is made up of housing, electrolyte, positive plate and negative plate, inserts porous insulating film between positive plate and the negative plate, and process is wound into electric core, charge into behind the housing of packing into to contain organic solvent electrolytic solution,
It is characterized in that the electrolyte employing contains the organic solvent mixture of iodine as the electrochemical reaction media, organic solvent comprises dimethoxy-ethane or dioxolane, or both mixtures, add iodine formation and contain organic solvent electrolytic solution in organic solvent, the concentration of iodine in organic solvent is 0.1mol/l～1.5mol/l.
2. the lithium battery that contains organic solvent electrolytic solution according to claim 1, it is characterized in that positive plate is the anodal powder of ferrous disulfide, binding agent, conductive additive, carbon black and graphite, organic solvent, stir after mixing mutually, scattered positive active material slurry is coated on the aluminium foil, rolls and be cut into suitable dimensions, negative plate is metal lithium bands or lithium-aluminium alloy band.
3. lithium battery preparation method who contains organic solvent electrolytic solution, negative plate is metal lithium bands or lithium-aluminium alloy band, positive plate is the pole piece that applies the ferrous disulfide active material, in the middle of negative plate and positive plate, insert and play the porous isolating membrane that separates the both positive and negative polarity effect, be wound into electric core and put into box hat, injection is sealed after containing organic solvent electrolytic solution
It is characterized in that containing the electrochemical reaction media of the organic solvent mixture of iodine as lithium/pyrite battery, organic solvent comprises dimethyl ethane or dioxolane, or both mixtures, in organic solvent, adding iodine, the concentration of iodine in organic solvent is 0.1mol/l～1.5mol/l.
4. the lithium battery preparation method who contains organic solvent electrolytic solution according to claim 3 is characterized in that the reaction of iodine lithium is quickened by the mode of heating, and temperature range is between 45 ℃～85 ℃.
5. the lithium battery preparation method who contains organic solvent electrolytic solution according to claim 3 is characterized in that the reaction of iodine lithium accelerates the formation speed of lithium iodide by little electric current forced electric discharge, and current range is between 0.001C ~ 0.5C.
6. the lithium battery preparation method who contains organic solvent electrolytic solution according to claim 3, it is characterized in that positive plate is the anodal powder of ferrous disulfide, binding agent Kynoar, conductive additive carbon black and graphite, organic solvent N, the N-dimethyl pyrrolidone, stir after mixing mutually, scattered positive active material slurry is coated on the aluminium foil.
7. the lithium battery preparation method who contains organic solvent electrolytic solution according to claim 3, it is characterized in that battery shelved for 1 week under 65 ℃ of high temperature after, battery take out at room temperature leave standstill 1 day after, battery is carried out stopping discharge behind the 1A pre-arcing 6min.
8. the lithium battery preparation method who contains organic solvent electrolytic solution according to claim 3, after it is characterized in that leaving standstill 1 day under the battery room temperature, 20ma stops discharge after being discharged to the voltage 1.6V of battery, at room temperature leave standstill 2 days after, battery is carried out stopping discharge behind the 1A pre-arcing 6min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008100262244A CN101227003B (en) | 2008-01-30 | 2008-01-30 | Lithium cell including organic solvent electrolytic solution |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008100262244A CN101227003B (en) | 2008-01-30 | 2008-01-30 | Lithium cell including organic solvent electrolytic solution |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101227003A true CN101227003A (en) | 2008-07-23 |
| CN101227003B CN101227003B (en) | 2011-05-25 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2008100262244A Active CN101227003B (en) | 2008-01-30 | 2008-01-30 | Lithium cell including organic solvent electrolytic solution |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101227003B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102456925A (en) * | 2010-10-21 | 2012-05-16 | 力佳电源科技(深圳)有限公司 | Method for preparing softly coated lithium manganese battery |
| CN103137981A (en) * | 2013-03-06 | 2013-06-05 | 潘群生 | Preparation method for anhydrous lithium iodide |
-
2008
- 2008-01-30 CN CN2008100262244A patent/CN101227003B/en active Active
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102456925A (en) * | 2010-10-21 | 2012-05-16 | 力佳电源科技(深圳)有限公司 | Method for preparing softly coated lithium manganese battery |
| CN102456925B (en) * | 2010-10-21 | 2014-09-24 | 力佳电源科技(深圳)有限公司 | Method for preparing softly coated lithium manganese battery |
| CN103137981A (en) * | 2013-03-06 | 2013-06-05 | 潘群生 | Preparation method for anhydrous lithium iodide |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101227003B (en) | 2011-05-25 |
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Owner name: GUANGZHOU GREAT POWER ENERGY + TECHNOLOGY CO., LTD Free format text: FORMER NAME: PENGHUI BATTERY CO., LTD., GUANGZHOU |
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| CP01 | Change in the name or title of a patent holder |
Address after: Sand village Panyu District Shawan Town, Guangzhou City, Guangdong province 511483 bunker first industrial zone Guangzhou Penghui Battery Co. Ltd. Patentee after: Guangzhou Great Power Energy & Technology Co., Ltd. Address before: Sand village Panyu District Shawan Town, Guangzhou City, Guangdong province 511483 bunker first industrial zone Guangzhou Penghui Battery Co. Ltd. Patentee before: Penghui Battery Co., Ltd., Guangzhou |
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Address after: 511483 Guangzhou City, Panyu District Shawan Town Liang Road (West Village section of No. 912) Patentee after: Guangzhou Great Power Energy & Technology Co., Ltd. Address before: Sand village Panyu District Shawan Town, Guangzhou City, Guangdong province 511483 bunker first industrial zone Guangzhou Penghui Battery Co. Ltd. Patentee before: Guangzhou Great Power Energy & Technology Co., Ltd. |
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Denomination of invention: Lithium cell including organic solvent electrolytic solution Effective date of registration: 20141208 Granted publication date: 20110525 Pledgee: Bank of China, Limited by Share Ltd, Guangzhou, Panyu branch Pledgor: Guangzhou Great Power Energy & Technology Co., Ltd. Registration number: 2014990001043 |
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Date of cancellation: 20170825 Granted publication date: 20110525 Pledgee: Bank of China, Limited by Share Ltd, Guangzhou, Panyu branch Pledgor: Guangzhou Great Power Energy & Technology Co., Ltd. Registration number: 2014990001043 |