CN105703003A - Comb-shaped polymer, electrolyte and composite electrode for lithium battery, and applications of electrolyte and composite electrode - Google Patents
Comb-shaped polymer, electrolyte and composite electrode for lithium battery, and applications of electrolyte and composite electrode Download PDFInfo
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Abstract
The invention discloses a comb-shaped polymer for a lithium battery, wherein the main chin and the side chain of the comb-shaped polymer both comprise polyethylene glycol structures; the polymer is mixed with a lithium salt to obtain a lithium battery electrolyte; and the electrolyte is mixed with an active material, a conductive agent and the like to obtain a lithium battery composite positive electrode. When the composite positive electrode is applied to an all-solid-state lithium battery, the interface resistance between the electrode and the electrolyte can be effectively lowered, and the high-current charging-discharging performance of the electrolyte can be greatly improved.
Description
Technical field
The invention belongs to technical field of lithium batteries, be specifically related to a kind of lithium battery comb-shaped polymer, electrolyte, combination electrode and application thereof。
Background technology
Lithium ion battery has energy density height, has extended cycle life, the advantage such as open-circuit voltage height, memory-less effect, as business-like high-efficiency energy-storage device, is widely used in daily productive life, such as the power supply of notebook computer, digital camera, mobile phone etc.。But, potential safety hazard such as flatulence and the blast etc. that in commercial li-ion battery, flammable organic electrolyte brings, remain problem and challenge that liquid electrolyte cannot be evaded, especially, when wideling popularize the large-scale application such as electric automobile and energy-accumulating power station field now, this problem is solved extremely urgent especially。
All-solid lithium-ion battery uses solid electrolyte to substitute the organic liquid electrolyte used in commercial li-ion battery, it is possible to fundamentally solve the safety problem of lithium ion battery。Research great majority currently, with respect to all-solid lithium-ion battery are concentrated on the solid electrolyte, and have been achieved for significant achievement, and the conductivity at room temperature of the solid electrolyte of a lot of systems is substantially accomplished 10-4S/cm, has substantially met the all-solid lithium-ion battery requirement to electrolytic conductivity。But utilizing the performance that solid electrolyte is assembled into battery but can not reach the standard of practicality, the interface contact that reason is between solid electrolyte and electrode material is very poor, increases interface resistance, have impact on battery performance。
Chinese patent: application publication number CN104479112A, the patent of invention in April 1 2015 Shen Qing Publication day disclose a kind of self-crosslinking comb-shaped polymer and lithium ion solid polymer dielectric, the main chain of this comb-shaped polymer is the polyolefin structure that can cross-link voluntarily, side chain is polyglycol chain, although adopt solid electrolyte prepared by this polymer to take into account good mechanical performance (5MPa) and higher electrical conductivity (10-4S/cm), but it yet suffers from following defect:
1, the cross-linking mechanism of the described polymer dielectric of this invention is the hot oxygen crosslinking of carbon-carbon double bond between main chain and main chain, will affect its film property and mechanical property when being reduced interface impedance by inorganic filler of adulterating or mixed with positive electrode further；
2, the PEG content of the described comb-shaped polymer of this invention is less, if side chain selects macromolecule PEG can cause that again crystallization makes electrical conductivity reduce。
Summary of the invention
It is an object of the invention to overcome what prior art existed cannot take into account mechanical strength and the defect of high ionic conductivity, it is provided that a kind of take into account interracial contact performance and mechanical performance and the lithium battery comb-shaped polymer of higher PEG content, electrolyte, combination electrode and application thereof can be obtained。
For realizing object above, the invention provides techniques below scheme:
A kind of lithium battery comb-shaped polymer, described polymer is polymer main, that side chain all contains polyethylene glycol structures, and its structural formula is as follows:
。
Described polymer is polymerized by triisocyanate coupling agent, main chain Polyethylene Glycol PEG, side chain poly glycol monomethyl ether MPEG, wherein, the molecular weight of described main chain Polyethylene Glycol PEG is 200～2000, and the molecular weight of side chain poly glycol monomethyl ether MPEG is 200～5000。
Described triisocyanate coupling agent is Toluene-2,4-diisocyanate, 4-diisocyanate trimer, 4,4,4-phenylmethane triisocyanate or hexamethylene diisocyanate trimer。
A kind of lithium cell electrolyte, described electrolyte contains above-mentioned polymer and lithium salts, and ratio [Li]/[EO] of the lithium ion in electrolyte and the ether oxygen atom in polymer is 1: 4～1: 25。
Described electrolyte also includes inorganic nano-particle and organic molecule plasticizer。
Described lithium salts is lithium perchlorate, lithium hexafluoro phosphate, LiBF4 or bis trifluoromethyl sulfimide lithium, described inorganic nano-particle is Nano particles of silicon dioxide, TiOx nano particle or boron oxide particle, and described organic molecule plasticizer is glycol dimethyl ether, diethylene glycol dimethyl ether or tetraethyleneglycol dimethyl ether。
A kind of lithium battery combination electrode, the raw material composition of described combination electrode includes above-mentioned electrolyte, active substance, binding agent and conductive agent, wherein, the mass fraction sum of described electrolyte and binding agent is 5%～40%, the mass fraction of described active substance is 40%～90%, and the mass fraction of described conductive agent is 5%～20%。
Described active substance is cobalt acid lithium, lithium nickelate, lithium vanadate, LiMn2O4, LiFePO4 or nickel-cobalt-manganese ternary material, and described binding agent is Kynoar, and described conductive agent is conductive black, electrically conductive graphite, SP-Li, Ketjen black, acetylene black or CNT。
The application in solid lithium battery of the described lithium cell electrolyte。
The application in solid lithium battery of the described lithium battery combination electrode。
Compared with prior art, the invention have the benefit that
1, the master of polymer of the present invention, side chain are polyethylene glycol structures, this polymer has higher PEG content and certain degree of cross linking, on the one hand, its higher PEG content ensure that have higher electrical conductivity with this polymer for the electrolyte that raw material obtains, on the other hand, certain degree of cross linking provides electrolytical mechanical strength, it is ensured that polymeric film also has good mechanical performance while having high conductivity, thus obtaining the electrolyte of excellent performance。Therefore, this invention ensures that polymeric film also has good mechanical performance while having high conductivity。
2, lithium battery anode composite of the present invention is mixed active substance and conductive agent etc. by described electrolyte and makes, and is that lithium ion provides transmission channel by introducing this electrolyte；By increasing the contact area between electrolyte and active substance, efficiently solve interface problem, shorten lithium ion migration distance in the positive active material of low lithium ion conductivity, ensure that positive active material sufficient redox reaction in battery charge and discharge process, be effectively increased the high rate during charging-discharging of lithium battery。Therefore, the present invention efficiently solves interface problem, improves the high rate during charging-discharging of lithium battery。
Detailed description of the invention
Below in conjunction with detailed description of the invention, the invention will be further described。
A kind of lithium battery comb-shaped polymer, described polymer is polymer main, that side chain all contains polyethylene glycol structures, and its structural formula is as follows:
。
Described polymer is polymerized by triisocyanate coupling agent, main chain Polyethylene Glycol PEG, side chain poly glycol monomethyl ether MPEG, wherein, the molecular weight of described main chain Polyethylene Glycol PEG is 200～2000, and the molecular weight of side chain poly glycol monomethyl ether MPEG is 200～5000。
Described triisocyanate coupling agent is Toluene-2,4-diisocyanate, 4-diisocyanate trimer, 4,4,4-phenylmethane triisocyanate or hexamethylene diisocyanate trimer。
A kind of lithium cell electrolyte, described electrolyte contains above-mentioned polymer and lithium salts, and ratio [Li]/[EO] of the lithium ion in electrolyte and the ether oxygen atom in polymer is 1: 4～1: 25。
Described electrolyte also includes inorganic nano-particle and organic molecule plasticizer。
Described lithium salts is lithium perchlorate, lithium hexafluoro phosphate, LiBF4 or bis trifluoromethyl sulfimide lithium, described inorganic nano-particle is Nano particles of silicon dioxide, TiOx nano particle or boron oxide particle, and described organic molecule plasticizer is glycol dimethyl ether, diethylene glycol dimethyl ether or tetraethyleneglycol dimethyl ether。
A kind of lithium battery combination electrode, the raw material composition of described combination electrode includes above-mentioned electrolyte, active substance, binding agent and conductive agent, wherein, the mass fraction sum of described electrolyte and binding agent is 5%～40%, the mass fraction of described active substance is 40%～90%, and the mass fraction of described conductive agent is 5%～20%。
Described active substance is cobalt acid lithium, lithium nickelate, lithium vanadate, LiMn2O4, LiFePO4 or nickel-cobalt-manganese ternary material, and described binding agent is Kynoar, and described conductive agent is conductive black, electrically conductive graphite, SP-Li, Ketjen black, acetylene black or CNT。
The application in solid lithium battery of the described lithium cell electrolyte。
The application in solid lithium battery of the described lithium battery combination electrode。
With the method that above-mentioned electrolyte prepares solid lithium battery for raw material, comprise the following steps successively:
The preparation of anode composite sheet: first described electrolyte, active substance, binding agent and conductive agent are disperseed in a solvent, ball milling mixing 11～13h again, finally carry out smear to obtain anode composite sheet, wherein, the mass fraction sum of described electrolyte and binding agent is 5%～40%, the mass fraction of described active substance is 40%～90%, and the mass fraction of described conductive agent is 5%～20%；
The assembling of solid lithium battery: first electrolyte is added drop-wise on anode composite sheet, to its vacuum drying 6～12h at 50～70 DEG C, there is electrolytical side to fit with dropping on anode composite sheet lithium sheet subsequently, finally carry out cell package and can obtain solid lithium battery。
Principles of the invention illustrates as follows:
The present invention proposes a kind of master, side chain is the Novel comb shaped polymer of Polyethylene Glycol PEG structure, the PEG content in polymer is saved by controlling the adjustable molecular weight of each polymerization single polymerization monomer, the degree of cross linking of polymer can be controlled by controlling the ingredient proportion of polymerization single polymerization monomer, ensure that polymer also has good mechanical performance while having high conductivity, thus obtaining the solid lithium battery electrolyte of excellent performance。This polymer prepared lithium battery combination electrode as raw material and is applied in solid lithium battery, can effectively reduce interface resistance between electrode and electrolyte, greatly improving the big electric current charging-discharging performances of lithium battery, and can at high temperature use。
With electrolyte of the present invention for raw material prepare solid lithium battery time, first electrolyte is mixed with anode composite sheet with active substance etc., electrolyte is added drop-wise on anode composite sheet final vacuum again to be dried, subsequently lithium sheet there is is electrolytical side to fit with dropping on anode composite sheet and carries out cell package, the method make polymer dielectric can direct film forming on anode composite sheet, thus strengthening contacting between anode composite sheet and polymer dielectric。
Embodiment 1:
A kind of lithium battery comb-shaped polymer, this polymer is polymer main, that side chain all contains polyethylene glycol structures, and this polymer is polymerized by triisocyanate coupling agent, main chain Polyethylene Glycol PEG, side chain poly glycol monomethyl ether MPEG, and its structural formula is as follows:
,
Wherein, described triisocyanate coupling agent is 4,4,4-phenylmethane triisocyanate TTI, and the molecular weight of described main chain Polyethylene Glycol PEG is 600, and the molecular weight of side chain poly glycol monomethyl ether MPEG is 1000, and the ratio of PEG, MPEG and TTI is 1: 1: 1。
A kind of lithium cell electrolyte, it contains above-mentioned polymer and lithium salts, and lithium salts is lithium perchlorate, and ratio [Li]/[EO] of the lithium ion in electrolyte and the ether oxygen atom in polymer is 1: 8。
A kind of lithium battery combination electrode, including above-mentioned electrolyte, active substance, binding agent and conductive agent, wherein, described binding agent is Kynoar, the mass fraction sum of described electrolyte and binding agent is 15%, and described active substance is cobalt acid lithium, and its mass fraction is 70%, described conductive agent is acetylene black, and its mass fraction is 15%。
With above-mentioned electrolyte for raw material prepare solid lithium battery time, carry out according to following steps successively:
The preparation of anode composite sheet: first described electrolyte, active substance, binding agent and conductive agent are disperseed in a solvent, then ball milling mixing 12h, finally carry out smear to obtain anode composite sheet；
The assembling of solid lithium battery: be first added drop-wise to by electrolyte on anode composite sheet, to its vacuum drying 6h at 60 DEG C, has electrolytical side to fit with dropping on anode composite sheet lithium sheet subsequently, finally carries out cell package and can obtain solid lithium battery。
In the present embodiment, described electrolytical hot strength is 1.5MPa, and electrical conductivity is 7 × 10-4S/cm, electrochemical window is 0～6V, with the solid lithium battery that above-mentioned electrolyte is prepared for raw material, carries out discharge and recharge at the voltage range 1C of 2.5～4.2V, and discharge capacity is 120mAh/g first, and after circulating 50 times, capacity is maintained at 80mAh/g。
Embodiment 2:
Step, with embodiment 1, is different in that:
In described polymer, the molecular weight of main chain Polyethylene Glycol PEG is 1000, TTI, the ratio of PEG and MPEG is 1: 1: 1.1；
In described electrolyte, lithium salts is bis trifluoromethyl sulfimide lithium, and ratio [Li]/[EO] of the lithium ion in electrolyte and the ether oxygen atom in polymer is 1: 4；
In described combination electrode, active substance is LiFePO4；
In the preparation process of described anode composite sheet, Ball-milling Time is 13h；
In the installation step of described solid lithium battery, vacuum drying temperature is 70 DEG C, and the vacuum drying time is 8h。
In the present embodiment, described electrolytical hot strength is 3MPa, and electrical conductivity is 4.5 × 10-4S/cm, electrochemical window is 0～6V, with the solid lithium battery that above-mentioned electrolyte is prepared for raw material, carries out discharge and recharge at the voltage range 1C of 2.5～4.2V, and discharge capacity is 125mAh/g first, and after circulating 50 times, capacity is maintained at 64mAh/g。
Embodiment 3:
Step, with embodiment 1, is different in that:
In described polymer, triisocyanate coupling agent is hexamethylene diisocyanate trimer HDItrimer, and the molecular weight of main chain Polyethylene Glycol PEG is 1000, the molecular weight of side chain poly glycol monomethyl ether MPEG is 2000, and the ratio of PEG, MPEG and HDItrimer is 1: 1: 1.2；
Described electrolyte also include glycol dimethyl ether that mass fraction is 10% and mass fraction be 3%, particle diameter be the Nano particles of silicon dioxide of 100nm, and lithium salts is Lithium biborate, ratio [Li]/[EO] of the lithium ion in electrolyte and the ether oxygen atom in polymer is 1: 12；
In described combination electrode, the mass fraction sum of electrolyte and binding agent is 25%, and the mass fraction of active substance is 60%, and conductive agent is Ketjen black, and its mass fraction is 15%；
In the present embodiment, described electrolytical hot strength is 7MPa, and electrical conductivity is 8.2 × 10-4S/cm, electrochemical window is 0～4.5V, with the solid lithium battery that above-mentioned electrolyte is prepared for raw material, carries out discharge and recharge at the voltage range 0.7C of 2.5～4.2V, and discharge capacity is 126mAh/g first, and after circulating 50 times, capacity is maintained at 94mAh/g。
Embodiment 4:
Step, with embodiment 1, is different in that:
In described polymer, triisocyanate coupling agent is Toluene-2,4-diisocyanate, 4-diisocyanate trimer TDItrimer, and the molecular weight of main chain Polyethylene Glycol PEG is 400, the molecular weight of side chain poly glycol monomethyl ether MPEG is 200, and the ratio of PEG, MPEG and TDItrimer is 1: 1: 1；
Described electrolyte also include tetraethyleneglycol dimethyl ether that mass fraction is 15% and mass fraction be 2%, particle diameter be the Nano particles of silicon dioxide of 10nm, and lithium salts is bis trifluoromethyl sulfimide lithium, ratio [Li]/[EO] of the lithium ion in electrolyte and the ether oxygen atom in polymer is 1: 10；
In described combination electrode, the mass fraction sum of electrolyte and binding agent is 20%, and active substance is lithium nickelate, and its mass fraction is 65%, and conductive agent is electrically conductive graphite, and its mass fraction is 15%；
In the present embodiment, described electrolytical hot strength is 1.9MPa, and electrical conductivity is 4.2 × 10-4S/cm, electrochemical window is 0～4.5V, with the solid lithium battery that above-mentioned electrolyte is prepared for raw material, carries out discharge and recharge at the voltage range 0.5C of 2.5～4.2V, and discharge capacity is 122mAh/g first, and after circulating 50 times, capacity is maintained at 78mAh/g。
Embodiment 5:
Step, with embodiment 1, is different in that:
In described polymer, the molecular weight of main chain Polyethylene Glycol PEG is 200, and the molecular weight of side chain poly glycol monomethyl ether MPEG is 1000；
Ratio [Li]/[EO] of the lithium ion in described electrolyte and the ether oxygen atom in polymer is 1: 12；
In described combination electrode, the mass fraction sum of electrolyte and binding agent is 10%, and active substance is LiMn2O4, and its mass fraction is 75%, and conductive agent is electrically conductive graphite, and its mass fraction is 15%；
In the preparation process of described anode composite sheet, Ball-milling Time is 11h；
In the installation step of described solid lithium battery, vacuum drying temperature is 50 DEG C, and the vacuum drying time is 12h。
In the present embodiment, described electrolytical hot strength is 2.4MPa, and electrical conductivity is 4.2 × 10-4S/cm, electrochemical window is 0～6V, with the solid lithium battery that above-mentioned electrolyte is prepared for raw material, carries out discharge and recharge at the voltage range 1C of 2.7～4.0V, and discharge capacity is 80mAh/g first, and after circulating 50 times, capacity is maintained at 43mAh/g。
Embodiment 6:
Step, with embodiment 1, is different in that:
In described polymer, triisocyanate coupling agent is hexamethylene diisocyanate trimer HDItrimer, and the molecular weight of main chain Polyethylene Glycol PEG is 1000, the molecular weight of side chain poly glycol monomethyl ether MPEG is 5000, and the ratio of PEG, MPEG and HDItrimer is 1: 1: 1.2；
Described electrolyte also include glycol dimethyl ether that mass fraction is 12% and mass fraction be 3%, particle diameter be the boron oxide particle of 100nm, ratio [Li]/[EO] of the lithium ion in electrolyte and the ether oxygen atom in polymer is 1: 25；
In described combination electrode, the mass fraction sum of electrolyte and binding agent is 5%, and active substance is lithium vanadate, and its mass fraction is 90%, and conductive agent is electrically conductive graphite, and its mass fraction is 5%；
In the present embodiment, described electrolytical hot strength is 7.1MPa, and electrical conductivity is 8.3 × 10-4S/cm, electrochemical window is 0～4.5V, with the solid lithium battery that above-mentioned electrolyte is prepared for raw material, carries out discharge and recharge at the voltage range 0.7C of 1.0～3.5V, and discharge capacity is 226mAh/g first, and after circulating 50 times, capacity is maintained at 87mAh/g。
Embodiment 7:
Step, with embodiment 1, is different in that:
In described polymer, the molecular weight of main chain Polyethylene Glycol PEG is 2000, and the molecular weight of side chain poly glycol monomethyl ether MPEG is 5000, PEG, the ratio of MPEG and TTI is 1: 1: 1.2；
Described electrolyte also include glycol dimethyl ether that mass fraction is 10% and mass fraction be 3%, particle diameter be the boron oxide particle of 100nm, and lithium salts is bis trifluoromethyl sulfimide lithium, ratio [Li]/[EO] of the lithium ion in electrolyte and the ether oxygen atom in polymer is 1: 12；
In described combination electrode, active substance is lithium nickelate；
In the present embodiment, described electrolytical hot strength is 7.0MPa, and electrical conductivity is 5.6 × 10-4S/cm, electrochemical window is 0～4.5V, with the solid lithium battery that above-mentioned electrolyte is prepared for raw material, carries out discharge and recharge at the voltage range 0.7C of 2.5～4.2V, and discharge capacity is 176mAh/g first, and after circulating 50 times, capacity is maintained at 117mAh/g。
Embodiment 8:
Step, with embodiment 1, is different in that:
In described polymer, triisocyanate coupling agent is Toluene-2,4-diisocyanate, 4-diisocyanate trimer TDItrimer, and the molecular weight of main chain Polyethylene Glycol PEG is 400, the molecular weight of side chain poly glycol monomethyl ether MPEG is 2000, and the ratio of PEG, MPEG and TDItrimer is 1: 1: 1.4；
Described electrolyte also include glycol dimethyl ether that mass fraction is 5% and mass fraction be 3%, particle diameter be the boron oxide particle of 100nm, and lithium salts is lithium hexafluoro phosphate, ratio [Li]/[EO] of the lithium ion in electrolyte and the ether oxygen atom in polymer is 1: 12；
In described combination electrode, active substance is LiFePO4；
In the present embodiment, described electrolytical hot strength is 8.0MPa, and electrical conductivity is 7.2 × 10-4S/cm, electrochemical window is 0～4.5V, with the solid lithium battery that above-mentioned electrolyte is prepared for raw material, carries out discharge and recharge at the voltage range 1C of 2.7～3.8V, and discharge capacity is 151mAh/g first, and after circulating 50 times, capacity is maintained at 98mAh/g。
For detecting the electrolytical resistance to elevated temperatures of the present invention, above-described embodiment electrolyte being carried out TG test, result display electrolyte starts to decompose more than 280 DEG C, it can thus be seen that electrolyte of the present invention has good resistance to elevated temperatures。
Claims (10)
1. a lithium battery comb-shaped polymer, it is characterised in that:
Described polymer is polymer main, that side chain all contains polyethylene glycol structures, and its structural formula is as follows
。
2. a kind of lithium battery comb-shaped polymer according to claim 1, it is characterized in that: described polymer is polymerized by triisocyanate coupling agent, main chain Polyethylene Glycol PEG, side chain poly glycol monomethyl ether MPEG, wherein, the molecular weight of described main chain Polyethylene Glycol PEG is 200～2000, and the molecular weight of side chain poly glycol monomethyl ether MPEG is 200～5000。
3. a kind of lithium battery comb-shaped polymer according to claim 1 and 2, it is characterized in that: described triisocyanate coupling agent is Toluene-2,4-diisocyanate, 4-diisocyanate trimer, 4,4,4-phenylmethane triisocyanate or hexamethylene diisocyanate trimer。
4. a lithium cell electrolyte, it is characterised in that: described electrolyte contains the polymer described in claim 1 and lithium salts, and ratio [Li]/[EO] of the lithium ion in electrolyte and the ether oxygen atom in polymer is 1: 4～1: 25。
5. a kind of lithium cell electrolyte according to claim 4, it is characterised in that: described electrolyte also includes inorganic nano-particle and organic molecule plasticizer。
6. a kind of lithium cell electrolyte according to claim 5, it is characterized in that: described lithium salts is lithium perchlorate, lithium hexafluoro phosphate, LiBF4 or bis trifluoromethyl sulfimide lithium, described inorganic nano-particle is Nano particles of silicon dioxide, TiOx nano particle or boron oxide particle, and described organic molecule plasticizer is glycol dimethyl ether, diethylene glycol dimethyl ether or tetraethyleneglycol dimethyl ether。
7. a lithium battery combination electrode, it is characterized in that: the raw material composition of described combination electrode includes the electrolyte described in claim 4, active substance, binding agent and conductive agent, wherein, the mass fraction sum of described electrolyte and binding agent is 5%～40%, the mass fraction of described active substance is 40%～90%, and the mass fraction of described conductive agent is 5%～20%。
8. a kind of lithium battery combination electrode according to claim 7, it is characterized in that: described active substance is cobalt acid lithium, lithium nickelate, lithium vanadate, LiMn2O4, LiFePO4 or nickel-cobalt-manganese ternary material, described binding agent is Kynoar, and described conductive agent is conductive black, electrically conductive graphite, SP-Li, Ketjen black, acetylene black or CNT。
9. the application in solid lithium battery of the lithium cell electrolyte described in claim 4。
10. lithium battery combination electrode application in solid lithium battery described in claim 7 or 8。
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Cited By (7)
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| CN106898812A (en) * | 2017-03-01 | 2017-06-27 | 北京当代经典科技有限公司 | A kind of solid polymer electrolyte and preparation method thereof and anode composite and solid lithium ion battery |
| CN106916308A (en) * | 2017-02-15 | 2017-07-04 | 北京当代经典科技有限公司 | Polymer and preparation method thereof and solid polymer electrolyte and all-solid lithium-ion battery |
| CN108258305A (en) * | 2016-12-28 | 2018-07-06 | 财团法人工业技术研究院 | Electrolyte and battery |
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| CN108258305A (en) * | 2016-12-28 | 2018-07-06 | 财团法人工业技术研究院 | Electrolyte and battery |
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| CN108306016A (en) * | 2018-02-02 | 2018-07-20 | 哈尔滨工业大学 | A method of cell positive material surface is modified using coupling agent |
| CN108878971A (en) * | 2018-07-03 | 2018-11-23 | 中国科学院宁波材料技术与工程研究所 | A kind of polymer dielectric and solid lithium battery with pectinate texture |
| JP7031100B1 (en) | 2020-12-14 | 2022-03-08 | 株式会社Abri | Gel electrolyte for lithium secondary battery, method for manufacturing lithium secondary battery and lithium secondary battery |
| JP2022093903A (en) * | 2020-12-14 | 2022-06-24 | 株式会社Abri | Gel electrolyte for lithium secondary battery, lithium secondary battery, and method for manufacturing lithium secondary battery |
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