CN102044705A - Method for manufacturing lithium ion polymer battery - Google Patents
Method for manufacturing lithium ion polymer battery Download PDFInfo
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- CN102044705A CN102044705A CN2010105917095A CN201010591709A CN102044705A CN 102044705 A CN102044705 A CN 102044705A CN 2010105917095 A CN2010105917095 A CN 2010105917095A CN 201010591709 A CN201010591709 A CN 201010591709A CN 102044705 A CN102044705 A CN 102044705A
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- electrolytic solution
- nonaqueous electrolytic
- carbonate
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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
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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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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Abstract
The invention relates to a method for manufacturing a lithium ion polymer battery, which comprises the conventional steps of: (1) winding anode and cathode pieces and a membrane to a battery cell and packing the battery cell in an aluminum-plastic packaging film; (2) conventionally and uniformly mixing to prepare a nonaqueous electrolytic solution containing lithium salt, film forming additive, polymer monomer and initiator; (3) conventionally infusing the nonaqueous electrolytic solution to the aluminum-plastic packaging film and sealing; and (4) forming a gel state of nonaqueous electrolytic solution at high temperature of 50-90 DEG C to obtain the lithium ion polymer battery. The invention effectively enhances the thermal stability of the electrolytic solution at high temperature, improves the thermal stability of the cathode SEI film and inhibits generation of gas.
Description
Technical field
The present invention relates to a kind of method of making battery, particularly a kind of method of making lithium ion polymer battery.
Background technology
Along with the continuous development of science and technology, new electronic equipment is urgent day by day for the demand in high-power rechargeable pond, and environmental protection has simultaneously also proposed new requirement to battery.The rechargeable pond mainly comprises lead-acid battery, nickel-cadmium cell, Ni-MH battery, lithium ion battery and fuel cell etc.Advantages such as wherein lithium ion battery has the voltage height, recycles often, memory time is long are the efficient green energy of generally acknowledging.
Polymer Li-ion battery all can distribute heat in running at electronic equipment, and hot environment causes battery cathode surface SEI film to decompose easily and electrolyte solvent on the both positive and negative polarity surface redox decomposition reaction takes place, and produces CO, CO
2, CH
4And C
2H
6Deng gas, make the deformation of polymer Li-ion battery bulging, battery capacity and cycle performance descend rapidly, and electronic equipment can be paralysed when serious because the deformation of battery also can be suffered destruction to a certain degree.
At present, for lithium ion battery bulging deformation problems, the main employing changes battery structure, adds method such as functional additive solve in electrolyte.At Journal of Power Sources 119 – 121 (2003) 833 – 837 example has been described, the battery that the battery deformation that the lamination mode is made is made less than winding method.Increase relief valve in addition, optimize electrode size and also can reduce the deformation of battery bulging.
Japan's publication (patent No. 96-64238A) adds calcium salt etc. in electrolyte.The method of foregoing description forms passivating film by add the organic or inorganic additive in electrolyte in the charcoal negative terminal surface, stops the reaction of negative pole and electrolyte solvent, reduces gas production, reduces battery bulging degree.
Yet all there is certain problem in these methods, as anti-bulging DeGrain, or additive itself at high temperature will decompose, or in the unstable decomposition of the passivating film of negative terminal surface formation, or the adding of additive has reduced electrode active material content, cause charging and discharging efficient and reduce decreased performance such as battery capacity, circulation.
Therefore, providing the method that a kind of technology is simple, obvious results is made lithium ion polymer battery, is one of these those skilled in the art problem that should address.
Summary of the invention
The objective of the invention is to overcome above-mentioned weak point, the method that a kind of technology is simple, easy to operate, obvious results is made lithium ion polymer battery is provided.
A kind of polymer Li-ion battery gel electrolyte is provided in the present invention especially, by utilizing the polymerized in-situ technology, electrolyte generation gelation with liquid state, make the side reaction between its decomposition that can stop the negative terminal surface passivating film and inhibition electrolyte solvent and the both positive and negative polarity, reduce the generation of gas, control cell thickness effectively, prevent distortion of battery bulging and cyclic deformation.
Implementation of the present invention is as follows for achieving the above object: a kind of method of making lithium ion polymer battery is characterized in that implementation step is as follows:
(1), and is encapsulated in the plastic-aluminum packaging film with positive/negative plate and membrane coil coiled battery;
Active material in the described positive plate is LiCoO
2, LiNiO
2, LiNi
xCo
yMn
zO
2(0≤x, y, z＜1), LiMn
2O
4, LiMnO
2, LiFePO
4In one or more mix arbitrarily evenly;
Active material in the described negative plate is one or both the evenly mixing arbitrarily in Delanium, the native graphite;
Described barrier film adopts polyolefin micropore barrier diaphragm, and its thickness is 9-40mm, and porosity is 25-50%;
(2) even routinely mixed preparing contains the nonaqueous electrolytic solution of lithium salts, film for additive, polymer monomer and initator;
The lithium salts that described nonaqueous electrolytic solution contains is LiPF
6, LiBF
4, LiBOB, LiN(CF
3SO
2)
2Or LiN(C
2F
5SO
2)
2Any mixing of wherein one or more, concentration are 0.4-1.2mol/L;
Film for additive in the described nonaqueous electrolytic solution is vinylene carbonate (VC), perhaps propylene sulfite (PS), and perhaps for both mix arbitrarily, it accounts for solvent quality % content is 0.5-4%;
Polymer monomer in the described nonaqueous electrolytic solution comprises polyethylene glycol oxide, the polyethylene glycol oxide of trifunctional, the propylene oxide oligomer monomer of two functional groups; It perhaps is the polymer monomer of methacrylate functional; It perhaps is the polymer monomer of acrylate-functional groups; Perhaps be wherein two or more arbitrary proportions mixing, content is 0.01%-8%;
Monomer initator in the described nonaqueous electrolytic solution comprises polyoxygenated benzoyl or azodiisobutyronitrile, and content is 0.01%-2%;
Main solvent in the described nonaqueous electrolytic solution is made up of cyclic carbonate and linear carbonate; Cyclic carbonate is mainly ethylene carbonate (EC), propene carbonate (PC); Linear carbonate is mainly diethyl carbonate (DEC), dimethyl carbonate (DMC), methyl ethyl carbonate (EMC), and electrolyte solvent is two or more any mixing wherein;
(3) described nonaqueous electrolytic solution is injected in the plastic-aluminum packaging film seals routinely;
(4) described nonaqueous electrolytic solution is at high temperature formed gel state, its temperature is 50-90 ℃, promptly makes.
The invention has the beneficial effects as follows: the present invention forms gel state under certain condition with containing the nonaqueous electrolytic solution of lithium salts, film for additive and polymer monomer and initator, thereby improve electrolyte thermal stability at high temperature, improve the thermal stability of negative pole SEI film, suppress the generation of gas.The gel electrolyte that polymer Li-ion battery among the present invention adopts has superior thermal stability, be fit to be applied in the hot environment, improve the thermal stability of negative pole SEI film, suppress the generation of gas, can effectively suppress the bulging distortion that battery takes place under the high temperature charge status, improve the capacity and the cycle performance of battery, improve the security performance of battery.Technology of the present invention is simple, operation standard, consistent, workable, applied range, effect highly significant.
Description of drawings
Fig. 1 is prepared battery capacity loss of the inventive method and cycle-index graph of relation;
Fig. 2 is prepared cell thickness of the inventive method and cycle-index graph of relation.
Embodiment
Below in conjunction with figure and preferred embodiment, to according to embodiment provided by the invention, details are as follows for feature:
Embodiment 1
A kind of method of making lithium ion polymer battery is characterized in that implementation step is as follows:
(1), and is encapsulated in the plastic-aluminum packaging film with positive/negative plate and membrane coil coiled battery;
Active material in the described positive plate is LiCoO
2, LiNiO
2, LiNi
xCo
yMn
zO
2(0≤x, y, z＜1), LiMn
2O
4, LiMnO
2, LiFePO
4In one or more mix arbitrarily evenly;
Active material in the described negative plate is one or both the evenly mixing arbitrarily in Delanium, the native graphite;
Described barrier film adopts polyolefin micropore barrier diaphragm, and its thickness is 9-40mm, and porosity is 25-50%.
(2) even routinely mixed preparing contains the nonaqueous electrolytic solution of lithium salts, film for additive, polymer monomer and initator;
The lithium salts that described nonaqueous electrolytic solution contains is LiPF
6, LiBF
4, LiBOB, LiN(CF
3SO
2)
2Or LiN(C
2F
5SO
2)
2Any mixing of wherein one or more, concentration are 0.4-1.2mol/L;
Film for additive in the described nonaqueous electrolytic solution is vinylene carbonate (VC), perhaps propylene sulfite (PS), and perhaps for both mix arbitrarily, it accounts for solvent quality % content is 0.5-4%;
Polymer monomer in the described nonaqueous electrolytic solution comprises polyethylene glycol oxide, the polyethylene glycol oxide of trifunctional, the propylene oxide oligomer monomer of two functional groups; It perhaps is the polymer monomer of methacrylate functional; It perhaps is the polymer monomer of acrylate-functional groups; Perhaps be wherein two or more arbitrary proportions mixing, content is 0.01%-8%;
Monomer initator in the described nonaqueous electrolytic solution comprises polyoxygenated benzoyl or azodiisobutyronitrile, and content is 0.01%-2%;
Main solvent in the described nonaqueous electrolytic solution is made up of cyclic carbonate and linear carbonate; Cyclic carbonate is mainly ethylene carbonate (EC), propene carbonate (PC); Linear carbonate is mainly diethyl carbonate (DEC), dimethyl carbonate (DMC), methyl ethyl carbonate (EMC), and electrolyte solvent is two or more any mixing wherein.
(3) described nonaqueous electrolytic solution is injected in the plastic-aluminum packaging film seals routinely.
(4) described nonaqueous electrolytic solution is at high temperature formed gel state, its temperature is 50-90 ℃, promptly makes.
Embodiment 2
Anodal preparation: with 92% LiCoO
2, 4% conductive black and 4%PVDF mix pulping in NMP, evenly be coated on the aluminium collector, last 100 ℃ of oven dry compactings are cut into 81mm * 650mm size, and welding of aluminum lug at one end.
The negative pole preparation: 92% MCMB, 4% conductive black and 4%PVDF are mixed pulping in NMP, evenly be coated on the copper collector, last 100 ℃ of oven dry compactings are cut into 83mm * 652mm size, and at one end weld the nickel lug.
The preparation of gel electrolyte: is that the 1:4:5 mixed is even with solvent EC, PC, DEC according to volume ratio, dissolves in 1mol/L LiPF
6Salt adds 2%VC, 0.8% PS film for additive, adds the polyoxygenated benzoyl of 1% monomer and 0.02%.
Positive pole, negative pole and membrane coil coiled utmost point group with preparing are encapsulated in the aluminium plastic packaging bag, remove redundant moisture through 85 ℃ of oven dry after 6 hours, inject the nonaqueous electrolytic solution for preparing, and carry out vacuum liquid-absorbing and seal.After the battery of having annotated liquid waited to leave standstill 12 hours, after electrolyte soaked into barrier film, both positive and negative polarity fully, the baking oven of putting into 70 ℃ was incubated 3 hours, makes electrolyte generation gelation, obtains polymer Li-ion battery.
Other is with embodiment 1.
Fig. 1 is the relation of the battery that makes of present embodiment between 60 ℃ of following 0.5C circulations of high temperature and capacitance loss, test voltage scope 3V-4.2V, and residual capacity is greater than 80% after 300 times.
Fig. 2 is the relation of the battery that makes of present embodiment between 60 ℃ of following 0.5C circulations of high temperature and cell thickness, test voltage scope 3V-4.2V, and the cell thickness bulging is less than 6% after 300 times.
Embodiment 3
Anodal preparation: with 93% LiCoO
2, 3% conductive black and 4%PVDF mix pulping in NMP, evenly be coated on the aluminium collector, last 100 ℃ of oven dry compactings are cut into 51mm * 551mm size, and welding of aluminum lug at one end.
The negative pole preparation: 90% MCMB, 4% conductive black and 6%PVDF are mixed pulping in NMP, evenly be coated on the copper collector, last 100 ℃ of oven dry compactings are cut into 53mm * 550mm size, and at one end weld the nickel lug.
The preparation of gel electrolyte: is that the 1:4:5 mixed is even with solvent EC, PC, DEC according to volume ratio, dissolves in 1mol/L LiPF
6Salt, VC, the PS film for additive of adding different content, the monomer and the polyoxygenated benzoyl of adding different content.
Positive pole, negative pole and membrane coil coiled electrode group with preparing are encapsulated in the plastic-aluminum packaging film, remove redundant moisture through 80 ℃ of oven dry after 8 hours, inject the nonaqueous electrolytic solution for preparing, and carry out vacuum liquid-absorbing and seal.After the battery of having annotated liquid waited to leave standstill 12 hours, electrolyte soaked into the barrier film that applies PVDF-HFP fully, put into 80 ℃ baking oven insulation 2 hours, made electrolyte be gel state in polymer substrate, obtained polymer Li-ion battery.
Other is with embodiment 1.
Table 1 is the relation between heterogeneity content and cycle capacity loss, cell thickness expand, and test condition is with 0.5C/0.5C circulation 300 times, voltage range 3V-4.2V under 60 ℃ of the high temperature.The result shows that the adding of 1%VC, 0.5% PS film for additive and 2% monomer and 0.1% initator can effectively suppress the bulging of battery under hot conditions, keeps higher capacity.
Relation between table 1 heterogeneity electrolyte and cycle capacity loss, cell thickness expand
| For example | Monomer | Initator | VC | PS | Residual capacity | The thickness bulging |
| Example 1 | 2% | 0.1% | 1% | 0.5% | 83% | 5.9% |
| Example 2 | 2% | 0.5% | 1% | 0.5% | 80% | 7.2% |
| Example 3 | 4% | 0.1% | 1% | 0.5% | 73% | 6.9% |
| Example 4 | 4% | 0.5% | 1% | 0.5% | 70% | 7.4% |
| Example 5 | 2% | 0.1% | 0 | 0.5% | 56% | 15.4% |
| Example 6 | 2% | 0.1% | 1% | 0% | 72% | 8.1% |
Operating procedure of the present invention is simple and practical, and is significant to guaranteeing battery performance, reduce production costs and enhancing productivity.
Above-mentioned detailed description of the method for this making lithium ion polymer battery being carried out with reference to embodiment is illustrative rather than determinate; Therefore in the variation and the modification that do not break away under the general plotting of the present invention, should belong within protection scope of the present invention.
Claims (1)
1. method of making lithium ion polymer battery is characterized in that implementation step is as follows:
(1), and is encapsulated in the plastic-aluminum packaging film with positive/negative plate and membrane coil coiled battery;
Active material in the described positive plate is LiCoO
2, LiNiO
2, LiNi
xCo
yMn
zO
2(0≤x, y, z＜1), LiMn
2O
4, LiMnO
2, LiFePO
4In one or more mix arbitrarily evenly;
Active material in the described negative plate is one or both the evenly mixing arbitrarily in Delanium, the native graphite;
Described barrier film adopts polyolefin micropore barrier diaphragm, and its thickness is 9-40mm, and porosity is 25-50%;
(2) even routinely mixed preparing contains the nonaqueous electrolytic solution of lithium salts, film for additive, polymer monomer and initator;
The lithium salts that described nonaqueous electrolytic solution contains is LiPF
6, LiBF
4, LiBOB, LiN(CF
3SO
2)
2Or LiN(C
2F
5SO
2)
2Any mixing of wherein one or more, concentration are 0.4-1.2mol/L;
Film for additive in the described nonaqueous electrolytic solution is vinylene carbonate (VC), perhaps propylene sulfite (PS), and perhaps for both mix arbitrarily, it accounts for solvent quality % content is 0.5-4%;
Polymer monomer in the described nonaqueous electrolytic solution comprises polyethylene glycol oxide, the polyethylene glycol oxide of trifunctional, the propylene oxide oligomer monomer of two functional groups; It perhaps is the polymer monomer of methacrylate functional; It perhaps is the polymer monomer of acrylate-functional groups; Perhaps be wherein two or more arbitrary proportions mixing, content is 0.01%-8%;
Monomer initator in the described nonaqueous electrolytic solution comprises polyoxygenated benzoyl or azodiisobutyronitrile, and content is 0.01%-2%;
Main solvent in the described nonaqueous electrolytic solution is made up of cyclic carbonate and linear carbonate; Cyclic carbonate is mainly ethylene carbonate (EC), propene carbonate (PC); Linear carbonate is mainly diethyl carbonate (DEC), dimethyl carbonate (DMC), methyl ethyl carbonate (EMC), and electrolyte solvent is two or more any mixing wherein;
(3) described nonaqueous electrolytic solution is injected in the plastic-aluminum packaging film seals routinely;
(4) described nonaqueous electrolytic solution is at high temperature formed gel state, its temperature is 50-90 ℃, promptly makes.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010105917095A CN102044705A (en) | 2010-12-16 | 2010-12-16 | Method for manufacturing lithium ion polymer battery |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010105917095A CN102044705A (en) | 2010-12-16 | 2010-12-16 | Method for manufacturing lithium ion polymer battery |
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| CN102044705A true CN102044705A (en) | 2011-05-04 |
Family
ID=43910632
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103022566A (en) * | 2012-12-27 | 2013-04-03 | 天津力神电池股份有限公司 | Soaking method for isolating membrane of ceramic isolating membrane lithium ion battery |
| CN103035943A (en) * | 2012-12-25 | 2013-04-10 | 天津市捷威动力工业有限公司 | Polymer electrolyte additive and gel polymer cell using same |
| CN103746142A (en) * | 2013-12-20 | 2014-04-23 | 厦门首能科技有限公司 | Gel electrolyte for lithium ion secondary battery and preparation method of gel electrolyte |
| CN104505533A (en) * | 2015-01-23 | 2015-04-08 | 杭州金色能源科技有限公司 | Gel electrolyte, lithium ion battery and preparation method for lithium ion battery |
| CN108511789A (en) * | 2018-04-24 | 2018-09-07 | 浙江大学 | A kind of method that full electrospinning prepares flexible secondary cell |
| CN108767328A (en) * | 2018-05-23 | 2018-11-06 | 广州大学 | A kind of preparation method of all-solid lithium-ion battery |
| CN108776311A (en) * | 2018-08-16 | 2018-11-09 | 江苏海基新能源股份有限公司 | A kind of quadrate lithium battery inflatable detection device and detection method |
| CN109546212A (en) * | 2018-11-26 | 2019-03-29 | 中南大学 | Solid polymer electrolyte preparation method and its solid secondary batteries |
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| CN1476123A (en) * | 2002-06-25 | 2004-02-18 | 夏普株式会社 | Gel electrolyte secondary cell and mfg. method thereof |
| CN1591930A (en) * | 2004-04-23 | 2005-03-09 | 东莞新能源电子科技有限公司 | Isolation diaphragm for secondary polymer lithium cell and its making method |
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2010
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| CN1476123A (en) * | 2002-06-25 | 2004-02-18 | 夏普株式会社 | Gel electrolyte secondary cell and mfg. method thereof |
| CN1591930A (en) * | 2004-04-23 | 2005-03-09 | 东莞新能源电子科技有限公司 | Isolation diaphragm for secondary polymer lithium cell and its making method |
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103035943A (en) * | 2012-12-25 | 2013-04-10 | 天津市捷威动力工业有限公司 | Polymer electrolyte additive and gel polymer cell using same |
| CN103035943B (en) * | 2012-12-25 | 2014-10-22 | 天津市捷威动力工业有限公司 | Polymer electrolyte additive and gel polymer cell using same |
| CN103022566A (en) * | 2012-12-27 | 2013-04-03 | 天津力神电池股份有限公司 | Soaking method for isolating membrane of ceramic isolating membrane lithium ion battery |
| CN103746142A (en) * | 2013-12-20 | 2014-04-23 | 厦门首能科技有限公司 | Gel electrolyte for lithium ion secondary battery and preparation method of gel electrolyte |
| CN103746142B (en) * | 2013-12-20 | 2017-02-22 | 厦门首能科技有限公司 | Gel electrolyte for lithium ion secondary battery and preparation method of gel electrolyte |
| CN104505533A (en) * | 2015-01-23 | 2015-04-08 | 杭州金色能源科技有限公司 | Gel electrolyte, lithium ion battery and preparation method for lithium ion battery |
| CN108511789A (en) * | 2018-04-24 | 2018-09-07 | 浙江大学 | A kind of method that full electrospinning prepares flexible secondary cell |
| CN108767328A (en) * | 2018-05-23 | 2018-11-06 | 广州大学 | A kind of preparation method of all-solid lithium-ion battery |
| JP2019204765A (en) * | 2018-05-23 | 2019-11-28 | 广州大学 | Method for manufacturing all-solid lithium ion battery |
| CN108776311A (en) * | 2018-08-16 | 2018-11-09 | 江苏海基新能源股份有限公司 | A kind of quadrate lithium battery inflatable detection device and detection method |
| CN109546212A (en) * | 2018-11-26 | 2019-03-29 | 中南大学 | Solid polymer electrolyte preparation method and its solid secondary batteries |
| CN109546212B (en) * | 2018-11-26 | 2022-05-20 | 广东聚圣科技有限公司 | Solid polymer electrolyte preparation method and solid secondary battery thereof |
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Application publication date: 20110504 |