CN101924243A - Lithium ion battery - Google Patents
Lithium ion battery Download PDFInfo
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- CN101924243A CN101924243A CN2010102433644A CN201010243364A CN101924243A CN 101924243 A CN101924243 A CN 101924243A CN 2010102433644 A CN2010102433644 A CN 2010102433644A CN 201010243364 A CN201010243364 A CN 201010243364A CN 101924243 A CN101924243 A CN 101924243A
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- lithium ion
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- 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 discloses a lithium ion battery. The lithium ion battery comprises a positive plate, a negative plate, an isolation membrane arranged between the positive plate and the negative plate and an electrolyte, wherein the positive plate comprises a positive current collector and a positive diaphragm which is attached to the positive current collector and contains a positive active substance; the negative plate comprises a negative current collector and a negative diaphragm which is attached to the negative current collector and contains a negative active substance; an electrolyte solvent contains dimethyl methylphosphonate; and the negative active substance is hard carbon. In the lithium ion battery, a structure that carbon layers of the hard carbon are randomly arranged reduces the destruction of the dimethyl methylphosphonate, and weakens a reduction reaction of the hard carbon and the dimethyl methylphosphonate in the formation process; and the first charge-discharge efficiency and capacity of the lithium ion battery are not reduced substantially due to the addition of the dimethyl methylphosphonate, and the safety of the lithium ion battery is improved.
Description
Technical field
The present invention relates to a kind of lithium ion battery, especially a kind of lithium ion battery with good safety energy and chemical property.
Background technology
Along with the development of information technology, the lithium ion battery with high-energy-density more and more is subjected to extensive favor.But there is potential safety hazard in use in lithium ion battery: because short circuit, overcharge, high temperature or other improper uses, cause that easily the lithium ion battery temperature raises and causes on fire, explosive incident.
In order to improve the security performance of lithium ion battery, can in electrolyte, add fire-retardant solvent methyl-phosphoric acid dimethyl ester.But, when methyl-phosphoric acid dimethyl ester is applied in the system that negative pole is a graphite, can be when changing into and graphite generation reduction reaction and cause graphite to be peeled off, make that the first charge-discharge efficiency of lithium ion battery and capacitance loss are very big, be difficult to take into account the security performance and the chemical property of lithium ion battery.
In view of this, necessary provide a kind of have good safety can and the lithium ion battery of chemical property.
Summary of the invention
The objective of the invention is to: a kind of lithium ion battery with good safety energy and chemical property is provided.
To achieve these goals, the invention provides a kind of lithium ion battery, it comprises positive plate, negative plate, is interval in the barrier film between positive plate and the negative plate, and electrolyte, wherein, positive plate comprises plus plate current-collecting body and attached to the anodal diaphragm that contains positive active material on the plus plate current-collecting body, negative plate comprises negative current collector and attached to the cathode membrane that contains negative electrode active material on the negative current collector, contain methyl-phosphoric acid dimethyl ester in the electrolyte solvent, negative electrode active material is a hard carbon.
With respect to prior art, lithium ion battery of the present invention has following useful technique effect: lithium ion battery of the present invention is applied to methyl-phosphoric acid dimethyl ester in the system that negative pole is a hard carbon, because the hard carbon carbon-coating has the structure of random ordering, so methyl-phosphoric acid dimethyl ester can not destroy carbon-coating easily and cause carbon-coating to be peeled off when changing into, the first charge-discharge efficiency and the capacity of lithium ion battery are unaffected, and lithium ion battery has good security performance and chemical property.
As a kind of improvement of lithium ion battery of the present invention, described electrolyte solvent all is a methyl-phosphoric acid dimethyl ester.
As a kind of improvement of lithium ion battery of the present invention, described electrolyte solvent is the mixture of methyl-phosphoric acid dimethyl ester and cyclic ester or chain ester, and the weight percentage of methyl-phosphoric acid dimethyl ester is 5%～100%.
As a kind of improvement of lithium ion battery of the present invention, described cyclic ester or chain ester are selected from ethylene carbonate, propene carbonate, methyl ethyl carbonate, dimethyl carbonate, diethyl carbonate, carbonic acid first propyl ester or its combination.
As a kind of improvement of lithium ion battery of the present invention, described positive active material is selected from cobalt acid lithium, LiMn2O4, LiFePO4, lithium nickel cobalt manganese or its combination.
As a kind of improvement of lithium ion battery of the present invention, described barrier film is three layers of barrier film of polypropylene, polyethylene/polypropylene.
As a kind of improvement of lithium ion battery of the present invention, the lithium salts in the described electrolyte is a lithium hexafluoro phosphate.
Description of drawings
Below in conjunction with specification drawings and specific embodiments, lithium ion battery of the present invention and useful technique effect thereof are elaborated, wherein:
Fig. 1 is the structure contrast schematic diagram of hard carbon and graphite.
Fig. 2 is the hot case empirical curve of comparative example 2 lithium ion batteries.
Fig. 3 is the hot case empirical curve of embodiment of the invention lithium ion battery.
Embodiment
Comparative example 1
The preparation of electrolyte: electrolyte is the lithium hexafluoro phosphate (LiPF of 1.2mol/L with concentration
6) be lithium salts, be solvent with the mixture of ethylene carbonate (EC), methyl ethyl carbonate (EMC) and dimethyl carbonate (DMC), the weight ratio of EC, EMC, DMC is EC: EMC: DMC=5: 2: 3.
The preparation of negative plate: as negative electrode active material, it accounts for 86% of cathode membrane total weight with graphite; As binding agent, it accounts for 6% of anodal diaphragm total weight with butadiene-styrene rubber (SBR); As conductive agent, it accounts for 8% of cathode membrane total weight with carbon dust (Super-p).With above-mentioned powder mixing and stirring in deionized water, make cathode size.Cathode size is coated on the negative current collector Copper Foil that thickness is 22 μ m equably, makes negative plate.
The preparation of positive plate: with the gram volume is the lithium nickel cobalt manganese (LiNi of 148mAh/g
(1/3)Co
(1//3)Mn
(1/3)) as positive active material, it accounts for 94% of anodal diaphragm total weight; As binding agent, it accounts for 2% of anodal diaphragm total weight with polyvinylidene fluoride (PVDF); As conductive agent, it respectively accounts for 2% of anodal diaphragm total weight with conductive carbon Super-p and KS-6.At N, mixing and stirring in the N-dimethyl pyrrolidone (NMP) is made anode sizing agent with above-mentioned powder.Anode sizing agent is coated on the plus plate current-collecting body aluminium foil that thickness is 22 μ m equably, makes positive plate.
The preparation of barrier film: barrier film adopts three layers of barrier film of polypropylene, polyethylene/polypropylene (PP/PE/PP), and thickness is 20 μ m.
The preparation of lithium ion battery: above-mentioned positive plate, barrier film and negative plate are superposeed successively, make the electric core of the about 930mAh of capacity by lamination or winding process, pack into electric core in the battery packages shell and inject aforementioned electrolyte, make comparative example 1 lithium ion battery through operation such as changing into.
Comparative example 2
The preparation of electrolyte: electrolyte is the lithium hexafluoro phosphate (LiPF of 1.2mol/L with concentration
6) be lithium salts, be solvent with the mixture of ethylene carbonate (EC), methyl ethyl carbonate (EMC) and dimethyl carbonate (DMC), the weight ratio of EC, EMC, DMC is EC: EMC: DMC=5: 2: 3.
The preparation of negative plate: as negative electrode active material, it accounts for 86% of cathode membrane total weight with hard carbon; As binding agent, it accounts for 6% of anodal diaphragm total weight with butadiene-styrene rubber (SBR); As conductive agent, it accounts for 8% of cathode membrane total weight with carbon dust (Super-p).With above-mentioned powder mixing and stirring in deionized water, make cathode size.Cathode size is coated on the negative current collector Copper Foil that thickness is 22 μ m equably, makes negative plate.
The preparation of positive plate: with the gram volume is the lithium nickel cobalt manganese (LiNi of 148mAh/g
(1/3)Co
(1//3)Mn
(1/3)) as positive active material, it accounts for 94% of anodal diaphragm total weight; As binding agent, it accounts for 2% of anodal diaphragm total weight with polyvinylidene fluoride (PVDF); As conductive agent, it respectively accounts for 2% of anodal diaphragm total weight with conductive carbon Super-p and KS-6.At N, mixing and stirring in the N-dimethyl pyrrolidone (NMP) is made anode sizing agent with above-mentioned powder.Anode sizing agent is coated on the plus plate current-collecting body aluminium foil that thickness is 22 μ m equably, makes positive plate.
The preparation of barrier film: barrier film adopts three layers of barrier film of polypropylene, polyethylene/polypropylene (PP/PE/PP), and thickness is 20 μ m.
The preparation of lithium ion battery: above-mentioned positive plate, barrier film and negative plate are superposeed successively, make the electric core of the about 930mAh of capacity by lamination or winding process, pack into electric core in the battery packages shell and inject aforementioned electrolyte, make comparative example 2 lithium ion batteries through operation such as changing into.
Comparative example 3
The preparation of electrolyte: electrolyte is the lithium hexafluoro phosphate (LiPF of 1.2mol/L with concentration
6) be lithium salts, be solvent with the mixture of ethylene carbonate (EC), methyl ethyl carbonate (EMC) and dimethyl carbonate (DMC), the weight ratio of EC, EMC, DMC is EC: EMC: DMC=5: 2: 3.In addition, also having added weight percentage in the electrolyte is 10% dimethyl methyl phosphonate (DMMP).
The preparation of negative plate: as negative electrode active material, it accounts for 86% of cathode membrane total weight with graphite; As binding agent, it accounts for 6% of anodal diaphragm total weight with butadiene-styrene rubber (SBR); As conductive agent, it accounts for 8% of cathode membrane total weight with carbon dust (Super-p).With above-mentioned powder mixing and stirring in deionized water, make cathode size, cathode size is uniformly coated on the Copper Foil that thickness is 22 μ m, make negative plate.
The preparation of positive plate: with the gram volume is the lithium nickel cobalt manganese (LiNi of 148mAh/g
(1/3)Co
(1//3)Mn
(1/3)) as positive active material, it accounts for 94% of anodal diaphragm total weight; As binding agent, it accounts for 2% of anodal diaphragm total weight with polyvinylidene fluoride (PVDF); As conductive agent, it respectively accounts for 2% of anodal diaphragm total weight with conductive carbon Super-p and KS-6.At N, mixing and stirring in the N-dimethyl pyrrolidone (NMP) is made anode sizing agent with above-mentioned powder.Anode sizing agent is coated on the aluminium foil that thickness is 22 μ m equably, makes positive plate.
The preparation of barrier film: barrier film adopts three layers of barrier film of polypropylene, polyethylene/polypropylene (PP/PE/PP), and thickness is 20 μ m.
The preparation of lithium ion battery: above-mentioned positive plate, barrier film and negative plate are superposeed successively, make the electric core of the about 930mAh of capacity by lamination or winding process, pack into electric core in the battery packages shell and inject aforementioned electrolyte, make comparative example 3 lithium ion batteries through operation such as changing into.
Embodiment
The preparation of electrolyte: electrolyte is the lithium hexafluoro phosphate (LiPF of 1.2mol/L with concentration
6) be lithium salts, be solvent with the mixture of ethylene carbonate (EC), methyl ethyl carbonate (EMC) and dimethyl carbonate (DMC), the weight ratio of EC, EMC, DMC is EC: EMC: DMC=5: 2: 3.In addition, also having added weight percentage in the electrolyte is 10% dimethyl methyl phosphonate (DMMP).
The preparation of negative plate: as negative electrode active material, it accounts for 86% of cathode membrane total weight with hard carbon; As binding agent, it accounts for 6% of anodal diaphragm total weight with butadiene-styrene rubber (SBR); As conductive agent, it accounts for 8% of cathode membrane total weight with carbon dust (Super-p).With above-mentioned powder mixing and stirring in deionized water, make cathode size.Cathode size is uniformly coated on the Copper Foil that thickness is 22 μ m, makes negative plate.
The preparation of positive plate: with the gram volume is the lithium nickel cobalt manganese (LiNi of 148mAh/g
(1/3)Co
(1//3)Mn
(1/3)) as positive active material, it accounts for 94% of anodal diaphragm total weight; As binding agent, it accounts for 2% of anodal diaphragm total weight with polyvinylidene fluoride (PVDF); As conductive agent, it respectively accounts for 2% of anodal diaphragm total weight with conductive carbon Super-p and KS-6.At N, mixing and stirring in the N-dimethyl pyrrolidone (NMP) is made anode sizing agent with above-mentioned powder.Anode sizing agent is coated on the aluminium foil that thickness is 22 μ m equably, makes positive plate.
The preparation of barrier film: barrier film adopts three layers of barrier film of polypropylene, polyethylene/polypropylene (PP/PE/PP), and thickness is 20 μ m.
The preparation of lithium ion battery: above-mentioned positive plate, barrier film and negative plate are superposeed successively, make the electric core of the about 930mAh of capacity by lamination or winding process, pack into electric core in the battery packages shell and inject aforementioned electrolyte, make lithium ion battery of the present invention through operation such as changing into.
See also shown in the table 1, compare with existing lithium ion battery, the first charge-discharge efficiency of lithium ion battery of the present invention and capacity are influenced hardly.
| Group | Initial charge capacity/mAh | Discharge capacity/mAh first | Efficient first |
| Comparative example 1 | 1175 | 930 | 79％ |
| Comparative example 2 | 1417 | 939 | 66％ |
| Comparative example 3 | 1050 | 960 | 91％ |
| Embodiment | 1535 | 977 | 64％ |
See also Fig. 2 and shown in Figure 3, in order to check the influence of methyl-phosphoric acid dimethyl ester (DMMP) to the lithium ion battery security energy, carry out 160 ℃ of hot casees experiments after comparative example 2 lithium ion batteries and lithium ion battery of the present invention completely be charged to 4.2V, be to be heated to 160 ℃ under the normal temperature, kept one hour, and saw whether battery is on fire, explode.From Fig. 2 and Fig. 3 as can be seen, though the voltage of comparative example 2 lithium ion batteries and embodiment of the invention lithium ion battery all reduces to zero, it is on fire that but embodiment of the invention lithium ion battery does not take place, and that comparative example 2 lithium ion batteries have taken place is on fire, nearly 400 ℃ of maximum temperature.
In conjunction with top description as can be seen: with respect to prior art, lithium ion battery of the present invention is applied to methyl-phosphoric acid dimethyl ester (DMMP) in the system that negative pole is a hard carbon, because the hard carbon carbon-coating has the structure (as shown in Figure 1) of random ordering, so methyl-phosphoric acid dimethyl ester when charging changes into (DMMP) can not destroy carbon-coating easily and cause carbon-coating to be peeled off, lithium ion battery has good security performance and chemical property simultaneously.
Need to prove, though only be that example describes positive active material in this manual with the lithium nickel cobalt manganese,, according to other embodiments of the invention, positive active material also can be cobalt acid lithium, LiMn2O4, LiFePO4, or the combination of above-mentioned substance.Though be that example describes electrolyte solvent only in this manual with ethylene carbonate, methyl ethyl carbonate, dimethyl carbonate, but, according to other embodiments of the invention, also can contain the combination of propene carbonate, diethyl carbonate, carbonic acid first propyl ester or above-mentioned substance in the electrolyte solvent.In addition, be that 10% methyl-phosphoric acid dimethyl ester is that the present invention will be described for example only in this specification to contain weight percentage in the electrolyte, but according to other embodiments of the invention, the weight percentage of methyl-phosphoric acid dimethyl ester also can be 5%～100%.
The announcement of book and instruction according to the above description, the technical staff of the technical field of the invention can also carry out suitable change and modification to above-mentioned execution mode.Therefore, the embodiment that discloses and describe above the present invention is not limited to also should fall in the protection range of claim of the present invention modifications and changes more of the present invention.In addition, although used some specific terms in this specification, these terms do not constitute any restriction to the present invention just for convenience of description.
Claims (7)
1. lithium ion battery, it comprises: positive plate, negative plate, be interval in the barrier film between positive plate and the negative plate, and electrolyte, wherein, positive plate comprises plus plate current-collecting body and attached to the anodal diaphragm that contains positive active material on the plus plate current-collecting body, negative plate comprises negative current collector and attached to the cathode membrane that contains negative electrode active material on the negative current collector, it is characterized in that: contain methyl-phosphoric acid dimethyl ester in the described electrolyte solvent, described negative electrode active material is a hard carbon.
2. lithium ion battery according to claim 1 is characterized in that: described electrolyte solvent all is a methyl-phosphoric acid dimethyl ester.
3. lithium ion battery according to claim 1 is characterized in that: described electrolyte solvent is the mixture of methyl-phosphoric acid dimethyl ester and cyclic ester or chain ester, and wherein, the weight percentage of methyl-phosphoric acid dimethyl ester is 5%～100%.
4. lithium ion battery according to claim 3 is characterized in that: described cyclic ester or chain ester are selected from ethylene carbonate, propene carbonate, methyl ethyl carbonate, dimethyl carbonate, diethyl carbonate, carbonic acid first propyl ester or its combination.
5. lithium ion battery according to claim 1 is characterized in that: described positive active material is selected from cobalt acid lithium, LiMn2O4, LiFePO4, lithium nickel cobalt manganese or its combination.
6. lithium ion battery according to claim 1 is characterized in that: described barrier film is three layers of barrier film of polypropylene, polyethylene/polypropylene.
7. lithium ion battery according to claim 1 is characterized in that: the lithium salts in the described electrolyte is a lithium hexafluoro phosphate.
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| CN2010102433644A CN101924243A (en) | 2010-07-29 | 2010-07-29 | Lithium ion battery |
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|---|---|---|---|
| CN2010102433644A CN101924243A (en) | 2010-07-29 | 2010-07-29 | Lithium ion battery |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102593417A (en) * | 2011-01-13 | 2012-07-18 | 苏州能斯特新能源有限公司 | Cylindrical lithium battery |
| CN102593504A (en) * | 2011-01-13 | 2012-07-18 | 苏州能斯特新能源有限公司 | Long-life lithium iron phosphate/hard carbon flexible package lithium battery |
| CN102593505A (en) * | 2011-01-13 | 2012-07-18 | 苏州能斯特新能源有限公司 | Square lithium battery |
| CN103730683A (en) * | 2013-12-27 | 2014-04-16 | 惠州亿纬锂能股份有限公司 | Lithium battery and preparation method thereof |
| CN104347846A (en) * | 2013-07-26 | 2015-02-11 | 浙江南博电源科技有限公司 | Preparation method for safety-improved nickel-cobalt lithium manganate positive electrode sheet |
| CN113366673A (en) * | 2021-03-25 | 2021-09-07 | 东莞新能源科技有限公司 | Electrochemical device and electronic device |
| CN114122497A (en) * | 2021-11-05 | 2022-03-01 | 复旦大学 | Lithium ion battery with high safety, low price and environmental protection |
| CN116632249A (en) * | 2023-07-26 | 2023-08-22 | 中创新航科技集团股份有限公司 | Lithium ion battery |
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| CN101662046A (en) * | 2009-09-18 | 2010-03-03 | 东莞新能源科技有限公司 | Lithium ion battery |
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| CN1191195C (en) * | 2000-04-27 | 2005-03-02 | 中国科学院物理研究所 | Pyrolyzed hard carbon material, preparation and its applications |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102593417A (en) * | 2011-01-13 | 2012-07-18 | 苏州能斯特新能源有限公司 | Cylindrical lithium battery |
| CN102593504A (en) * | 2011-01-13 | 2012-07-18 | 苏州能斯特新能源有限公司 | Long-life lithium iron phosphate/hard carbon flexible package lithium battery |
| CN102593505A (en) * | 2011-01-13 | 2012-07-18 | 苏州能斯特新能源有限公司 | Square lithium battery |
| CN104347846A (en) * | 2013-07-26 | 2015-02-11 | 浙江南博电源科技有限公司 | Preparation method for safety-improved nickel-cobalt lithium manganate positive electrode sheet |
| CN103730683A (en) * | 2013-12-27 | 2014-04-16 | 惠州亿纬锂能股份有限公司 | Lithium battery and preparation method thereof |
| CN113366673A (en) * | 2021-03-25 | 2021-09-07 | 东莞新能源科技有限公司 | Electrochemical device and electronic device |
| CN114122497A (en) * | 2021-11-05 | 2022-03-01 | 复旦大学 | Lithium ion battery with high safety, low price and environmental protection |
| CN116632249A (en) * | 2023-07-26 | 2023-08-22 | 中创新航科技集团股份有限公司 | Lithium ion battery |
| CN116632249B (en) * | 2023-07-26 | 2023-09-29 | 中创新航科技集团股份有限公司 | Lithium ion battery |
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Application publication date: 20101222 |