CN101325270B - Flatulence-proof electrolytic solution for iron phosphate lithium battery - Google Patents
Flatulence-proof electrolytic solution for iron phosphate lithium battery Download PDFInfo
- Publication number
- CN101325270B CN101325270B CN2008100317622A CN200810031762A CN101325270B CN 101325270 B CN101325270 B CN 101325270B CN 2008100317622 A CN2008100317622 A CN 2008100317622A CN 200810031762 A CN200810031762 A CN 200810031762A CN 101325270 B CN101325270 B CN 101325270B
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- CN
- China
- Prior art keywords
- iron phosphate
- carbonate
- main body
- lithium battery
- ethylene carbonate
- 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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- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 title claims abstract description 13
- 239000008151 electrolyte solution Substances 0.000 title claims description 7
- 206010016766 flatulence Diseases 0.000 title claims description 7
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000003792 electrolyte Substances 0.000 claims abstract description 24
- 239000002904 solvent Substances 0.000 claims abstract description 24
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 12
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 12
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims abstract description 11
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000013538 functional additive Substances 0.000 claims abstract description 3
- 229910052744 lithium Inorganic materials 0.000 claims description 19
- 239000000654 additive Substances 0.000 claims description 11
- 230000000996 additive effect Effects 0.000 claims description 11
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 10
- -1 ethyl-methyl Chemical group 0.000 claims description 10
- 150000002148 esters Chemical class 0.000 claims description 7
- 229910013870 LiPF 6 Inorganic materials 0.000 claims description 5
- WYMSBXTXOHUIGT-UHFFFAOYSA-N paraoxon Chemical compound CCOP(=O)(OCC)OC1=CC=C([N+]([O-])=O)C=C1 WYMSBXTXOHUIGT-UHFFFAOYSA-N 0.000 claims description 3
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 abstract 3
- 229910052808 lithium carbonate Inorganic materials 0.000 abstract 3
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 abstract 2
- 230000002579 anti-swelling effect Effects 0.000 abstract 2
- 230000008961 swelling Effects 0.000 abstract 2
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 abstract 1
- 239000000203 mixture Substances 0.000 abstract 1
- 239000005955 Ferric phosphate Substances 0.000 description 9
- 229940032958 ferric phosphate Drugs 0.000 description 9
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 9
- 229910000399 iron(III) phosphate Inorganic materials 0.000 description 9
- 238000000034 method Methods 0.000 description 7
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 6
- 239000000470 constituent Substances 0.000 description 6
- 229910052493 LiFePO4 Inorganic materials 0.000 description 4
- 239000011149 active material Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000003797 solvolysis reaction Methods 0.000 description 1
- 230000004083 survival effect Effects 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 relates to an anti-swelling electrolyte for lithium iron phosphate batteries, which comprises the following components: (1) a mixture composed of at least three solvents with high dielectric constant and low viscosity selected from ethylene carbonate, diethyl carbonate, dimethyl carbonate and ethylmethyl carbonate as a major solvent with the total content of 95%-98%; (2) fluoroethylene carbonate and battery-grade Li2CO3 as the functional additives for preventing swelling and bulging, wherein the contents of fluoroethylene carbonate and battery-grade Li2CO3 are 1%-3% and 1%-2% respectively and the total content thereof is 2-5%; and (3) the concentration of the lithium salts is 0.8-1.2 mol/L. The anti-swelling electrolyte for the lithium iron phosphate batteries can absorb the moisture in the electrode so as to prevent the batteries from swelling and bulging. Additionally, a dense SEI film is formed on the surface of the cathode to effectively improve the electrochemical performance of the lithium iron phosphate battery. Furthermore, Li2CO3 in the electrolyte can effectively increase the capacity per gram of lithium iron phosphate, and further increase the energy density of the lithium iron phosphate battery.
Description
Technical field
The present invention relates to a kind of lithium-ion battery electrolytes, particularly relate to a kind of flatulence-proof electrolytic solution for iron phosphate lithium battery.
Background technology
Energy crisis, shortage of resources, environmental pollution be human survival face sternly complete challenge, seeking secondary energy sources clean, renewable, resource-conserving is the vital task that realizes that human social needs to be resolved hurrily.
LiFePO4 has extended cycle life because its security performance is good, and is environmentally friendly, extensively thought the first-selected positive electrode of electrokinetic cell of future generation by people.But lithium iron phosphate positive material also has a fatal shortcoming, and that is exactly that conductivity is low, and this shortcoming has greatly influenced LiFePO
4Application.
At present, in order to overcome this shortcoming, people increase the specific area of material or coat the carbon that one deck can conduct electricity, to improve its electric conductivity by the preparation ultra-fine grain.Having brought a new problem again but particle is tiny, is exactly suction easily in manufacturing process.As everyone knows, the harm of moisture in the manufacturing process of lithium ion battery is very big.Particularly, be easy to so produce ballooning, thus, the chemical property and the security performance of ferric phosphate lithium cell produced serious negative effect for LiFePO4.Therefore, the inflatable problem of ferric phosphate lithium cell has badly influenced LiFePO
4The application of battery and development.
Summary of the invention
The objective of the invention is to overcome the above-mentioned defective of prior art, provide a kind of have prevent that the electrolyte of ballooning function from appearring in ferric phosphate lithium cell.
The present invention purpose be achieved through the following technical solutions; Its component is as follows: (1) is the main body solvent with at least three kinds mixed liquor in the low viscous solvent of high-k such as ethylene carbonate (EC), diethyl carbonate (DEC), dimethyl carbonate (DMC), the ethyl-methyl carbonic ester (EMC), with the effective dissolving of assurance electrolyte lithium salts and the stable formation of electrode surface SEI film, its total content is 95-98%; (2) functional additive of anti-inflatable and bulging is selected fluorinated ethylene carbonate (FEC) and LITHIUM BATTERY Li
2CO
3, the preferred 1-3% of fluorinated ethylene carbonate constituent content, LITHIUM BATTERY Li
2CO
3The preferred 1-2% of component, the two adds up to content is 2-5%; (3) lithium salt is 0.8-1.2mol/L.
The preferred three component solvents of described main body solvent, wherein, ethylene carbonate is 28%-42%, diethyl carbonate 25%-32%, dimethyl carbonate is 28%-42%, ethyl-methyl carbonic ester 25%-38%; Three's total percentage still is 95-98%.
The preferred LiPF of lithium salts
6
Described percentage all is weight percentage, and it is 100% basic as calculating adding up to weight with main body solvent and additive.
Fluorinated ethylene carbonate in the present invention's the electrolyte (FEC) and LITHIUM BATTERY Li
2CO
3In charge and discharge process, the moisture that can absorb in the electrode well to be carried secretly, and form abundant SEI film in negative terminal surface, not only can solve well like this because the ballooning that moisture causes, thereby the cell thickness that suppresses to be caused by inflatable increases, and abundant SEI film, can improve the chemical property of ferric phosphate lithium cell effectively; Li in the electrolyte
2CO
3, can be effectively with electrolyte in the HF reaction, and then reduce HF with from LiFePO
4The Li that deviates from
+Reaction, thereby the gram volume of raising LiFePO4, and then the energy density of raising ferric phosphate lithium cell.
Embodiment
The invention will be further described below in conjunction with embodiment.
Embodiment 1
Electrolyte main body solvent adopts ethylene carbonate (EC), dimethyl carbonate (DMC), ethyl-methyl carbonic ester (EMC), and its constituent content is respectively 30%, 35% and 32%; Additive fluorinated ethylene carbonate (FEC) and LITHIUM BATTERY Li
2CO
3Content be respectively 2% and 1%; Lithium salts (LiPF
6) concentration is 1.0mol/L.According to said components proportioning and conventional electrolyte quota method preparation.
Embodiment 2
Electrolyte main body solvent adopts ethylene carbonate (EC), dimethyl carbonate (DMC), ethyl-methyl carbonic ester (DEC), and its constituent content is respectively 40%, 30% and 28%.Additive fluorinated ethylene carbonate (FEC) and LITHIUM BATTERY Li
2CO
3Content be respectively 1% and 1%.Lithium salt is 1.1mol/L.According to said components and conventional electrolyte quota method preparation.
Embodiment 3
Electrolyte main body solvent adopts ethylene carbonate (EC), dimethyl carbonate (DMC), ethyl-methyl carbonic ester (EMC), and its constituent content is respectively 30%, 30% and 35%.Additive fluorinated ethylene carbonate (FEC) and LITHIUM BATTERY Li
2CO
3Content be respectively 3% and 2%.Lithium salts (LiPF
6) lithium salt is 0.8mol/L.According to said components proportioning and conventional electrolyte quota method preparation.
Embodiment 4
Electrolyte main body solvent adopts ethylene carbonate (EC), dimethyl carbonate (DMC), ethyl-methyl carbonic ester (EMC), and its constituent content is respectively 30%, 40% and 27%.Additive fluorinated ethylene carbonate (FEC) and LITHIUM BATTERY Li
2CO
3Content be respectively 1.5% and 1.5%.Lithium salts (LiPF
6) lithium salt is 1.0mol/L.According to said components proportioning and conventional electrolyte quota method preparation.
Embodiment 5
Electrolyte main body solvent adopts ethylene carbonate (EC), dimethyl carbonate (DMC), ethyl-methyl carbonic ester (EMC), and its constituent content is respectively 35%, 35% and 29%.Additive fluorinated ethylene carbonate (FEC) and LITHIUM BATTERY Li
2CO
3Content respectively be 0.5%.Lithium salts (LiPF
6) concentration is 1.2mol/L.According to said components proportioning and conventional electrolyte quota method preparation.
Electrolyte according to the foregoing description 1-5 preparation is applied to 226770 type ferric phosphate lithium cells, is made into battery according to the battery production process of routine, tests its thickness and gram volume, and thickness is as shown in table 1, and gram volume is as shown in table 2.
Table 1 embodiment 1-5 electrolyte is applied to the thickness of 226770 ferric phosphate lithium cells
| Embodiment | 1 | 2 | 3 | 4 | 5 | Conventional method |
| Thickness (mm) | 22.45 | 22.62 | 22.56 | 22.64 | 22.62 | 23.57 |
Table 2 embodiment 1-5 electrolyte is applied to the gram volume of 226770 ferric phosphate lithium cells
| Embodiment | 1 | 2 | 3 | 4 | 5 | Conventional method |
| Gram volume (mAh/g) | 132 | 133 | 134 | 131 | 133 | 126 |
Described gram volume detection method: at first write down the weight of pole piece in each battery and calculate LiFePO
4The weight of active material treats that battery changes into the capacity that obtains entire cell cashier's office in a shop after forming and capacity dividing finishes in BK7064 (10A) type, with battery capacity divided by LiFePO
4The weight of active material just obtains LiFePO
4The gram volume of active material.
As seen from Table 1, the cell thickness that is caused by inflatable reduces to some extent, shows described additive in charge and discharge process, and moisture that can absorb in the electrode effectively really to be carried secretly and the micro-molecular gas that is produced by solvolysis prevent that inflatable and bulging phenomenon from taking place.
As seen from Table 2, the electrolyte of embodiment 1-5 is applied to 226770 ferric phosphate lithium cells, and the gram volume of LiFePO4 can improve 3.97%-6.35%.
Claims (4)
1. flatulence-proof electrolytic solution for iron phosphate lithium battery, it is characterized in that, be made of following component: (1) is the main body solvent with at least three kinds the mixed liquor that is selected from the low viscous solvent ethylene carbonate of high-k, diethyl carbonate, dimethyl carbonate and the ethyl-methyl carbonic ester, and total content is 95-98%; (2) functional additive of anti-inflatable and bulging is fluorinated ethylene carbonate and LITHIUM BATTERY Li
2CO
3, fluorinated ethylene carbonate content is 1-3%, LITHIUM BATTERY Li
2CO
3Content is 1-2%, and the two adds up to content is 2-5%; (3) electrolyte lithium salt LiPF
6Concentration is 0.8-1.2mol/L;
Described percentage is weight percentage, and it is 100% basic as calculating adding up to weight with main body solvent and additive.
2. flatulence-proof electrolytic solution for iron phosphate lithium battery according to claim 1 is characterized in that, described main body solvent is three component solvents, component and proportioning are, ethylene carbonate is 28%-42%, ethyl-methyl carbonic ester 25%-32%, and dimethyl carbonate is 28%-42%;
Described percentage is weight percentage, and it is 100% basic as calculating adding up to weight with main body solvent and additive.
3. flatulence-proof electrolytic solution for iron phosphate lithium battery according to claim 1 is characterized in that, described main body solvent is three component solvents, component and proportioning are, ethylene carbonate is 28%-42%, diethyl carbonate 25%-32%, ethyl-methyl carbonic ester 25%-38%;
Described percentage is weight percentage, and it is 100% basic as calculating adding up to weight with main body solvent and additive.
4. flatulence-proof electrolytic solution for iron phosphate lithium battery according to claim 1 is characterized in that, described main body solvent is three component solvents, component and proportioning are, ethylene carbonate is 28%-42%, and dimethyl carbonate is 28%-42%, diethyl carbonate 25%-32%;
Described percentage is weight percentage, and it is 100% basic as calculating adding up to weight with main body solvent and additive.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008100317622A CN101325270B (en) | 2008-07-15 | 2008-07-15 | Flatulence-proof electrolytic solution for iron phosphate lithium battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008100317622A CN101325270B (en) | 2008-07-15 | 2008-07-15 | Flatulence-proof electrolytic solution for iron phosphate lithium battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101325270A CN101325270A (en) | 2008-12-17 |
| CN101325270B true CN101325270B (en) | 2011-05-18 |
Family
ID=40188685
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2008100317622A Active CN101325270B (en) | 2008-07-15 | 2008-07-15 | Flatulence-proof electrolytic solution for iron phosphate lithium battery |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101325270B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101841061A (en) * | 2010-05-10 | 2010-09-22 | 陈韵吉 | Low-temperature electrolyte of lithium iron phosphate power battery and preparation method thereof |
| CN102593510B (en) * | 2011-01-06 | 2016-03-09 | 深圳市比克电池有限公司 | A kind of electrolyte and lithium ion battery |
-
2008
- 2008-07-15 CN CN2008100317622A patent/CN101325270B/en active Active
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| Publication number | Publication date |
|---|---|
| CN101325270A (en) | 2008-12-17 |
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| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| ASS | Succession or assignment of patent right |
Owner name: HUNAN SHANSHAN NEW MATERIALS CO., LTD. Free format text: FORMER OWNER: CHANGSHA SHANSHAN POWER BATTERY CO., LTD. Effective date: 20091023 |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20091023 Address after: Hunan province Changsha Lugu high tech Industrial Park District Lu Tin Road No. 17-8 post encoding: 410205 Applicant after: HUNAN SHANSHAN ADVANCED MATERIAL CO.,LTD. Address before: Hunan province Changsha City Lugu Lu Feng Road No. 42 post encoding: 410205 Applicant before: CHANGSHA SHANSHAN POWER BATTERY Co.,Ltd. |
|
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C56 | Change in the name or address of the patentee | ||
| CP03 | Change of name, title or address |
Address after: 410205 Hunan province Changsha hi tech Development Zone, Lu Valley Lu Tin Road No. 17-8 Patentee after: HUNAN SHANSHAN ENERGY TECHNOLOGY Co.,Ltd. Address before: 410205 Hunan province Changsha Lugu high tech Industrial Park District Lu Tin Road No. 17-8 Patentee before: HUNAN SHANSHAN ADVANCED MATERIAL CO.,LTD. |
|
| CP01 | Change in the name or title of a patent holder | ||
| CP01 | Change in the name or title of a patent holder |
Address after: No. 17-8, Lutian Road, high tech Development Zone, Changsha City, Hunan Province, 410205 Patentee after: BASF Shanshan battery material Co.,Ltd. Address before: No. 17-8, Lutian Road, high tech Development Zone, Changsha City, Hunan Province, 410205 Patentee before: Hunan Shanshan Energy Technology Co.,Ltd. Address after: No. 17-8, Lutian Road, high tech Development Zone, Changsha City, Hunan Province, 410205 Patentee after: Hunan Shanshan Energy Technology Co.,Ltd. Address before: No. 17-8, Lutian Road, high tech Development Zone, Changsha City, Hunan Province, 410205 Patentee before: HUNAN SHANSHAN ENERGY TECHNOLOGY Co.,Ltd. |