CN111162313A - 一种聚合物电解质及锂离子电池 - Google Patents
一种聚合物电解质及锂离子电池 Download PDFInfo
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- CN111162313A CN111162313A CN201911339937.0A CN201911339937A CN111162313A CN 111162313 A CN111162313 A CN 111162313A CN 201911339937 A CN201911339937 A CN 201911339937A CN 111162313 A CN111162313 A CN 111162313A
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- Prior art keywords
- fluoro
- acid
- carboxylic acid
- polymer electrolyte
- hydroxy
- Prior art date
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 42
- 239000005518 polymer electrolyte Substances 0.000 title claims abstract description 38
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 20
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 20
- 239000000376 reactant Substances 0.000 claims abstract description 19
- 239000011259 mixed solution Substances 0.000 claims abstract description 16
- 239000013538 functional additive Substances 0.000 claims abstract description 15
- 239000003960 organic solvent Substances 0.000 claims abstract description 14
- 229920001002 functional polymer Polymers 0.000 claims abstract description 12
- 238000011065 in-situ storage Methods 0.000 claims abstract description 11
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims description 24
- -1 hydroxy ester Chemical class 0.000 claims description 23
- 125000000524 functional group Chemical group 0.000 claims description 22
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 18
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 18
- 239000000654 additive Substances 0.000 claims description 15
- 230000000996 additive effect Effects 0.000 claims description 15
- 125000005587 carbonate group Chemical group 0.000 claims description 9
- 239000003153 chemical reaction reagent Substances 0.000 claims description 9
- 125000004122 cyclic group Chemical group 0.000 claims description 9
- 150000002148 esters Chemical group 0.000 claims description 8
- 125000001153 fluoro group Chemical group F* 0.000 claims description 8
- 150000003839 salts Chemical class 0.000 claims description 6
- RGLZXVNOHDUMRJ-UHFFFAOYSA-N 2-(trifluoromethyl)pyrimidine-5-carboxylic acid Chemical compound OC(=O)C1=CN=C(C(F)(F)F)N=C1 RGLZXVNOHDUMRJ-UHFFFAOYSA-N 0.000 claims description 5
- BAYGVMXZJBFEMB-UHFFFAOYSA-N 4-(trifluoromethyl)phenol Chemical compound OC1=CC=C(C(F)(F)F)C=C1 BAYGVMXZJBFEMB-UHFFFAOYSA-N 0.000 claims description 5
- ABDBNWQRPYOPDF-UHFFFAOYSA-N carbonofluoridic acid Chemical group OC(F)=O ABDBNWQRPYOPDF-UHFFFAOYSA-N 0.000 claims description 5
- BHRSRGUVJGTOBA-UHFFFAOYSA-N 2-(trifluoromethyl)quinoline-4-carboxylic acid Chemical compound C1=CC=C2C(C(=O)O)=CC(C(F)(F)F)=NC2=C1 BHRSRGUVJGTOBA-UHFFFAOYSA-N 0.000 claims description 4
- APHPXZJIUTVQNC-UHFFFAOYSA-N 3-borono-5-fluorobenzoic acid Chemical compound OB(O)C1=CC(F)=CC(C(O)=O)=C1 APHPXZJIUTVQNC-UHFFFAOYSA-N 0.000 claims description 4
- NBAHQCCWEKHGTD-UHFFFAOYSA-N 5-fluoro-1h-pyrimidin-6-one Chemical compound OC1=NC=NC=C1F NBAHQCCWEKHGTD-UHFFFAOYSA-N 0.000 claims description 4
- HTELWJVKZKSAQI-UHFFFAOYSA-N 8-fluoro-1h-quinolin-4-one Chemical compound N1C=CC(=O)C2=C1C(F)=CC=C2 HTELWJVKZKSAQI-UHFFFAOYSA-N 0.000 claims description 4
- NKCVNYJQLIWBHK-UHFFFAOYSA-N carbonodiperoxoic acid Chemical group OOC(=O)OO NKCVNYJQLIWBHK-UHFFFAOYSA-N 0.000 claims description 4
- ZFTFAPZRGNKQPU-UHFFFAOYSA-N dicarbonic acid Chemical compound OC(=O)OC(O)=O ZFTFAPZRGNKQPU-UHFFFAOYSA-N 0.000 claims description 4
- AQYSYJUIMQTRMV-UHFFFAOYSA-N hypofluorous acid Chemical group FO AQYSYJUIMQTRMV-UHFFFAOYSA-N 0.000 claims description 4
- MVQOOJNHXHBCGK-UHFFFAOYSA-N 1-(2-fluorophenyl)cyclopropane-1-carboxylic acid Chemical compound C=1C=CC=C(F)C=1C1(C(=O)O)CC1 MVQOOJNHXHBCGK-UHFFFAOYSA-N 0.000 claims description 3
- OKOPJQWSINWAMU-UHFFFAOYSA-N 1-(3-fluorophenyl)cyclopropane-1-carboxylic acid Chemical compound C=1C=CC(F)=CC=1C1(C(=O)O)CC1 OKOPJQWSINWAMU-UHFFFAOYSA-N 0.000 claims description 3
- NGVPHOXWSFIYNV-UHFFFAOYSA-N 1-(4-fluorophenyl)cyclopropane-1-carboxylic acid Chemical compound C=1C=C(F)C=CC=1C1(C(=O)O)CC1 NGVPHOXWSFIYNV-UHFFFAOYSA-N 0.000 claims description 3
- DGQRYPPBAJNZFZ-UHFFFAOYSA-N 1-(trifluoromethyl)cyclopentane-1-carboxylic acid Chemical compound OC(=O)C1(C(F)(F)F)CCCC1 DGQRYPPBAJNZFZ-UHFFFAOYSA-N 0.000 claims description 3
- FMVANIKYUYQABO-UHFFFAOYSA-N 2-borono-5-fluorobenzoic acid Chemical compound OB(O)C1=CC=C(F)C=C1C(O)=O FMVANIKYUYQABO-UHFFFAOYSA-N 0.000 claims description 3
- YUWKPDBHJFNMAD-UHFFFAOYSA-N 2-fluoroterephthalic acid Chemical group OC(=O)C1=CC=C(C(O)=O)C(F)=C1 YUWKPDBHJFNMAD-UHFFFAOYSA-N 0.000 claims description 3
- DMWLBOPLZYJGPT-UHFFFAOYSA-N 3-(trifluoromethyl)pyridine-2-carboxylic acid Chemical compound OC(=O)C1=NC=CC=C1C(F)(F)F DMWLBOPLZYJGPT-UHFFFAOYSA-N 0.000 claims description 3
- ZBVKRLUVHQGYGA-UHFFFAOYSA-N 3-(trifluoromethyl)quinoline-8-carboxylic acid Chemical compound FC(F)(F)C1=CN=C2C(C(=O)O)=CC=CC2=C1 ZBVKRLUVHQGYGA-UHFFFAOYSA-N 0.000 claims description 3
- YLZPFWJYAFZZHF-UHFFFAOYSA-N 3-borono-4-fluorobenzoic acid Chemical compound OB(O)C1=CC(C(O)=O)=CC=C1F YLZPFWJYAFZZHF-UHFFFAOYSA-N 0.000 claims description 3
- YGGNZDRZJWUYRO-UHFFFAOYSA-N 4-(trifluoromethyl)quinoline-2-carboxylic acid Chemical compound C1=CC=CC2=NC(C(=O)O)=CC(C(F)(F)F)=C21 YGGNZDRZJWUYRO-UHFFFAOYSA-N 0.000 claims description 3
- CZDWJVSOQOMYGC-UHFFFAOYSA-N 4-borono-2-fluorobenzoic acid Chemical compound OB(O)C1=CC=C(C(O)=O)C(F)=C1 CZDWJVSOQOMYGC-UHFFFAOYSA-N 0.000 claims description 3
- GDLCLHCOKQFBPI-UHFFFAOYSA-N 4-fluoro-1h-indole-7-carboxylic acid Chemical compound OC(=O)C1=CC=C(F)C2=C1NC=C2 GDLCLHCOKQFBPI-UHFFFAOYSA-N 0.000 claims description 3
- NJHGVAYLDHROPT-UHFFFAOYSA-N 5-(trifluoromethyl)pyridine-2-carboxylic acid Chemical compound OC(=O)C1=CC=C(C(F)(F)F)C=N1 NJHGVAYLDHROPT-UHFFFAOYSA-N 0.000 claims description 3
- DKYUCRYPZALEMP-UHFFFAOYSA-N 5-amino-2-fluoropyridine-4-carboxylic acid Chemical compound NC1=CN=C(F)C=C1C(O)=O DKYUCRYPZALEMP-UHFFFAOYSA-N 0.000 claims description 3
- JTKFIIQGMVKDNZ-UHFFFAOYSA-N 5-fluoropyridine-2-carboxylic acid Chemical compound OC(=O)C1=CC=C(F)C=N1 JTKFIIQGMVKDNZ-UHFFFAOYSA-N 0.000 claims description 3
- BXZSBDDOYIWMGC-UHFFFAOYSA-N 5-fluoropyridine-3-carboxylic acid Chemical compound OC(=O)C1=CN=CC(F)=C1 BXZSBDDOYIWMGC-UHFFFAOYSA-N 0.000 claims description 3
- YHXLEKUJMPEQAJ-UHFFFAOYSA-N 5-fluoroquinolin-8-ol Chemical compound C1=CN=C2C(O)=CC=C(F)C2=C1 YHXLEKUJMPEQAJ-UHFFFAOYSA-N 0.000 claims description 3
- CDWGDLKZKCYUFO-UHFFFAOYSA-N 6-(trifluoromethyl)-1h-indole-2-carboxylic acid Chemical compound C1=C(C(F)(F)F)C=C2NC(C(=O)O)=CC2=C1 CDWGDLKZKCYUFO-UHFFFAOYSA-N 0.000 claims description 3
- KFWMUBBPUAWTPO-UHFFFAOYSA-N 6-fluoro-4-methylpyridine-3-carboxylic acid Chemical compound CC1=CC(F)=NC=C1C(O)=O KFWMUBBPUAWTPO-UHFFFAOYSA-N 0.000 claims description 3
- KCEJQAATYWQMMQ-UHFFFAOYSA-N 6-fluoro-4-oxo-1h-quinoline-3-carboxylic acid Chemical compound C1=C(F)C=C2C(=O)C(C(=O)O)=CNC2=C1 KCEJQAATYWQMMQ-UHFFFAOYSA-N 0.000 claims description 3
- ZLHGUGJJHJJVHV-UHFFFAOYSA-N 7-fluoro-1h-quinolin-4-one Chemical compound N1C=CC(=O)C=2C1=CC(F)=CC=2 ZLHGUGJJHJJVHV-UHFFFAOYSA-N 0.000 claims description 3
- DOMJYWCXCVFKCA-UHFFFAOYSA-N methyl 4-amino-3-fluorobenzoate Chemical compound COC(=O)C1=CC=C(N)C(F)=C1 DOMJYWCXCVFKCA-UHFFFAOYSA-N 0.000 claims description 3
- REIVHYDACHXPNH-UHFFFAOYSA-N 2-fluoro-4-hydroxybenzonitrile Chemical compound OC1=CC=C(C#N)C(F)=C1 REIVHYDACHXPNH-UHFFFAOYSA-N 0.000 claims description 2
- MCOSBFKOUQAIJS-UHFFFAOYSA-N 2-fluoro-5-(trifluoromethyl)phenol Chemical compound OC1=CC(C(F)(F)F)=CC=C1F MCOSBFKOUQAIJS-UHFFFAOYSA-N 0.000 claims description 2
- YEBHNFDMNFHZFF-UHFFFAOYSA-N 2-fluoro-6-hydroxybenzonitrile Chemical compound OC1=CC=CC(F)=C1C#N YEBHNFDMNFHZFF-UHFFFAOYSA-N 0.000 claims description 2
- UEQRKEWMEMJXQO-UHFFFAOYSA-N 2-fluoropyridin-3-ol Chemical compound OC1=CC=CN=C1F UEQRKEWMEMJXQO-UHFFFAOYSA-N 0.000 claims description 2
- UGEJOEBBMPOJMT-UHFFFAOYSA-N 3-(trifluoromethyl)phenol Chemical compound OC1=CC=CC(C(F)(F)F)=C1 UGEJOEBBMPOJMT-UHFFFAOYSA-N 0.000 claims description 2
- CISUDJRBCKKAGX-UHFFFAOYSA-N 3-fluoro-1h-pyridin-2-one Chemical compound OC1=NC=CC=C1F CISUDJRBCKKAGX-UHFFFAOYSA-N 0.000 claims description 2
- IXBHZARBEOBOTB-UHFFFAOYSA-N 3-fluoro-4-(hydroxymethyl)phenol Chemical compound OCC1=CC=C(O)C=C1F IXBHZARBEOBOTB-UHFFFAOYSA-N 0.000 claims description 2
- ATVNHLQIIAOSEM-UHFFFAOYSA-N 3-fluoro-5-hydroxybenzonitrile Chemical compound OC1=CC(F)=CC(C#N)=C1 ATVNHLQIIAOSEM-UHFFFAOYSA-N 0.000 claims description 2
- QSJNKJGPJVOGPK-UHFFFAOYSA-N 4-(4-fluorophenyl)phenol Chemical group C1=CC(O)=CC=C1C1=CC=C(F)C=C1 QSJNKJGPJVOGPK-UHFFFAOYSA-N 0.000 claims description 2
- XSRUCRGHYLPMHK-UHFFFAOYSA-N 4-fluoro-1h-pyridin-2-one Chemical compound OC1=CC(F)=CC=N1 XSRUCRGHYLPMHK-UHFFFAOYSA-N 0.000 claims description 2
- LKTBMKIXEOGAGF-UHFFFAOYSA-N 4-fluoro-3-hydroxybenzonitrile Chemical compound OC1=CC(C#N)=CC=C1F LKTBMKIXEOGAGF-UHFFFAOYSA-N 0.000 claims description 2
- HPABFFGQPLJKBP-UHFFFAOYSA-N 5-fluoro-1H-pyrimidin-2-one Chemical compound OC1=NC=C(F)C=N1 HPABFFGQPLJKBP-UHFFFAOYSA-N 0.000 claims description 2
- KLULSYPVWLJZAO-UHFFFAOYSA-N 5-fluoro-1h-pyridin-2-one Chemical compound OC1=CC=C(F)C=N1 KLULSYPVWLJZAO-UHFFFAOYSA-N 0.000 claims description 2
- LYFBZGKZAZBANN-UHFFFAOYSA-N 5-fluorobenzene-1,3-diol Chemical compound OC1=CC(O)=CC(F)=C1 LYFBZGKZAZBANN-UHFFFAOYSA-N 0.000 claims description 2
- IUFLFKASIHPKNZ-UHFFFAOYSA-N 5-fluoropyridin-3-ol Chemical compound OC1=CN=CC(F)=C1 IUFLFKASIHPKNZ-UHFFFAOYSA-N 0.000 claims description 2
- AJRUXHIEYSYRQJ-UHFFFAOYSA-N 6-fluoro-1h-pyridin-2-one Chemical compound OC1=CC=CC(F)=N1 AJRUXHIEYSYRQJ-UHFFFAOYSA-N 0.000 claims description 2
- BYZXOYSEYWCLOK-UHFFFAOYSA-N 6-fluoro-1h-quinolin-4-one Chemical compound C1=C(F)C=C2C(O)=CC=NC2=C1 BYZXOYSEYWCLOK-UHFFFAOYSA-N 0.000 claims description 2
- HTRLNWYWOKWCLV-UHFFFAOYSA-N 6-fluoropyridin-3-ol Chemical compound OC1=CC=C(F)N=C1 HTRLNWYWOKWCLV-UHFFFAOYSA-N 0.000 claims description 2
- LDCRHJNNQVTBNY-UHFFFAOYSA-N 7-fluoroquinolin-8-ol Chemical compound C1=CN=C2C(O)=C(F)C=CC2=C1 LDCRHJNNQVTBNY-UHFFFAOYSA-N 0.000 claims description 2
- YPQLFJODEKMJEF-UHFFFAOYSA-N hydroxyflutamide Chemical group CC(C)(O)C(=O)NC1=CC=C([N+]([O-])=O)C(C(F)(F)F)=C1 YPQLFJODEKMJEF-UHFFFAOYSA-N 0.000 claims description 2
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- 238000004519 manufacturing process Methods 0.000 claims 1
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- 239000003792 electrolyte Substances 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 9
- 229910052744 lithium Inorganic materials 0.000 description 9
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- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 6
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- 238000002955 isolation Methods 0.000 description 5
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- 229910001486 lithium perchlorate Inorganic materials 0.000 description 4
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- 229910013872 LiPF Inorganic materials 0.000 description 3
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- 229920002319 Poly(methyl acrylate) Polymers 0.000 description 3
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- 229910052742 iron Inorganic materials 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 238000004806 packaging method and process Methods 0.000 description 3
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Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0065—Solid electrolytes
- H01M2300/0082—Organic polymers
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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
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Abstract
本发明属于锂离子电池技术领域，尤其涉及一种聚合物电解质及锂离子电池。该聚合物电解质的制备方法，包括：(1)按重量份数计，将5～90份有机溶剂溶解0.01～27份功能聚合物制备均匀混合A体系；(2)将A体系、锂盐、功能添加剂和功能反应剂混合均匀，即得到混合液；(3)将所述混合液进行原位聚合得到聚合物电解质。本发明制备的聚合物电解质能有效改善锂离子电池的安全性，具有广泛的应用前景。
Description
技术领域
本发明属于锂离子电池技术领域，尤其涉及一种聚合物电解质及锂离子电池。
背景技术
锂离子电池具有能量密度高、循环寿命长、绿色无污染等特点，目前已经在动力、数码、储能等领域得到应用。但是由于锂离子电池采液态易燃电解液，在实际使用过程中会存在漏液、热失控、起火爆炸等安全问题。
目前为改善锂离子电池安全问题，目前采用了PTC极耳、PTC正极极片、高安全性电解液、高安全性隔膜等技术方案。但是以上技术方案并未从根本上解决锂离子电池的安全问题和市场对于高能量密度的需求。固态锂离子电池作为最可能实现产业化的下一代锂离子电池，固态锂离子电池具有高能量密度和安全性等特点。固态电池主要由固态正极、固态负极和固态电解质构成，其中固态电解质主要有聚合物电解质、硫化物电解质、氧化物电解质、氢化物电解质。硫化物电解质电导率高，但是存在对环境氛围敏感、界面接触差等问题；氧化物电解质存在界面接触差、难以加工等问题；氢化物电解质存在易还原且与正极相容性差等问题。聚合物电解质状态可分类为全固态聚合物电解质、半固态电解质和凝胶电解质。全固态聚合物电解质存在电导率低、电化学稳定性差等问题，半固态电解质和凝胶电解质具有电导率高、电化学稳定性佳，具有良好的应用潜力。
发明内容
本发明公开了一种相对于现有的锂电池，安全性能更优的锂离子电池，具体的，本发明的技术方案如下：
本发明第一个方面公开了一种聚合物电解质。所述聚合物电解质包括氟结构：
所述R52-R60均为有机官能团，所述氟结构的分子量为500～10W。
优选的，所述聚合物电解质还包括碳酸酯结构；
其中所述碳酸酯结构为：
所述R32-R40均为有机官能团，所述碳酸酯结构的分子量为500～10W。
优选的，所述聚合物电解质还包括下式酯结构中的一种；
所述R32-R39、R44-R51均为有机官能团，所述酯结构的分子量为500～10W。
具体的，该聚合物电解质以有机溶剂、功能聚合物、锂盐、功能添加剂和功能反应剂为原料来制备，在此过程中主要涉及以下几种反应：
本发明第二个方面公开了一种聚合物电解质的制备方法，包括：
(1)按重量份数计，将5～90份有机溶剂溶解0.01～27份功能聚合物制备均匀混合A体系；
(2)将A体系、锂盐、功能添加剂和功能反应剂混合均匀，即得到混合液；
(3)将所述混合液进行原位聚合得到聚合物电解质。
优选的，所述有机溶剂为羟基碳酸酯、羧基碳酸酯、羟基酯或羧基酯。
其中羟基碳酸酯结构为
R1和R2为有机官能团，R1和R2可以单独或互相结合形成环状结构，优选的，所述羟基碳酸酯为羟甲基二氧杂戊环酮、乙基4-(羟基甲基)-2,6-二甲氧基苯基碳酸酯、过氧化二碳酸二-3-甲氧丁酯、(S)-4-(甲氧甲基)-1,3-二氧杂环戊烷-2-酮、羟甲基二氧杂戊环酮、D-半乳醛环3,4-碳酸、(R)-(+)-4-(甲氧甲基)-1,3-二氧六环基-2-酮、2,3-O-羰基-A-D-吡喃甘露糖、2,5-二氧杂己二酸二甲酯中的一种或几种。
其中羧基碳酸酯结构为
R3和R4为有机官能团，R3和R4可以单独或互相结合形成环状结构，优选的，所述羧基碳酸酯为4-羧苯基正丁基碳酸酯、降冰片烯-2,3-二羧基亚胺基对硝基苄基碳酸酯、降冰片烯-2,3-二羧基亚胺基叔丁基碳酸酯、2-[(乙氧基羰基)氧基]-3-羟基丁二酸(CAS号：799271-79-7)、1,3-二恶烷-5-羧酸，5-甲基-2-氧代(9CI)(CAS号：1181216-85-2)、1,3-二恶英-4-羧酸，5-(1-甲基乙基)-2-氧代-(9CI)(CAS号：188525-84-0)、1,3-二氧戊环-4-羧酸，5-甲基-2-氧代-甲酯(4S反式)(CAS号：160816-87-5)、2,5-二氧-1,3-二氧戊环-4-甲酸(CAS号:112726-72-4)、甲氧基羰基乙酸、2-[(乙氧基羰基)氧基]-3-羟基丁二酸(CAS号：799271-79-7)、异丁基羰基乳糖酸酐(CAS号：74216-73-2)、乳酸碳酸乙酯(CAS号：5700-72-1)中的一种或几种。
其中羟基酯结构为
R5、R6、R7和R8为有机官能团，R5、R6、R7和R8可以单独或互相结合形成环状结构，优选的，所述羟基酯结构为3-羟基-苯乙酸乙酯、3-羟基苯甲酸甲酯、3-羟基苯甲酸乙酯、2-羟基苯乙酸甲酯、羟基三甲基乙酸甲酯、3-羟基己酸甲酯、3-羟基己酸乙酯、羟基乙酸丁酯、3-羟基丁酸乙酯、5-羟基烟酸甲酯、6-羟基烟酸甲酯、6-羟基-2-萘甲酯、乙醇酸甲酯、4-羟基丁酸甲酯、3-羟基丙酸甲酯、3-羟基丙酸乙酯、(±)-3-羟基-r-丁内酯、2-羟基癸酸甲酯、5-羟基戊酸甲酯、乙醇酸乙酯、乙醇酸苯甲酯、3-羟基噻吩-2-羧酸乙酯、6-羟基己酸甲酯、6-羟基己酸乙酯、1,2-乙二醇单乙酸酯、3,4-二羟基苯乙醇醋酸、3-羟基辛酸乙酯、4-羟基丁酸乙酯、2-羟基戊酸乙酯、3-羟基吡啶-4-羧酸乙酯、聚乙二醇甲基丙烯酸酯、聚乙二醇单硬脂酸酯、3-羟基-3-甲基丁酸乙酯、聚乙烯醇肉桂酸酯、聚甘油蓖麻醇酯、聚酯多元醇、聚己内酯多元醇和聚碳酸酯二醇中的一种或几种。
其中羧基酯结构为
R9、R10、R11和R12为有机官能团，R9、R10、R11和R12可以单独或互相结合形成环状结构，优选的，所述羧基酯结构为3-羧基甲基哌嗪-1-羧基酸叔-丁基酯、6-[4-(叔丁氧羰酰)哌嗪-1-YL]烟酸、3-(4-羧基-苯基)-哌啶-1-羧酸叔丁酯、4-(4-羧基苯基)哌嗪-1-羧酸叔丁酯、3-羧基甲氧基-哌啶-1-羧酸叔丁酯、4-羧基苯硼酸频那醇酯、(R)-(-)-5-氧代-2-四氢呋喃羧酸、2-羧基苯基硼酸频哪醇酯、4,5-二羧基-十五内酯、4-羧基苯乙酸甲酯、1,1-环丙基二甲酸单甲酯、2,2-二甲基丙二酸单乙酯、2-氧代-2H-吡喃-3-甲酸、2-氧代-6-戊基-2H-吡喃-3-羧酸、甲基丙二酸氢、1,1-环丙基二甲酸单甲酯、丙二酸单叔丁酯、7-羟基香豆素-3-羧酸、6-氯-2-氧代-2H-苯并吡喃-3-羧酸、丙二酸单乙酯、3,4-二氢-8-甲氧基-2-氧代-2H-苯并吡喃-3-甲酸、L-天门冬氨酸-4-叔丁基酯、Cbz-L-天冬氨酸-4-苄酯、反式-2-(甲氧羰基)环己烷羧酸、四氢-5-氧代-2-苯基呋喃-3-羧酸、芴甲氧羰基-天冬氨酸-4环己脂、2-(2-甲氧基苯基)-5-氧代四氢呋喃-3-羧酸、2-甲氧羰基环己烷-1-羧酸、琥珀酸单乙酯、丁二酸单甲酯(琥珀酸单甲酯)、7-羟基-4-甲基香豆素-3-乙酸、Fmoc-L-天冬氨酸beta-叔丁酯、BOC-3-氨基-2-(萘-2-基)丙酸、Boc-L-天冬氨酸1-苄酯、乙酰氧基乙酸、2-(4-溴苯基)-2-(异丁酰氧基)乙酸、(-)-O-乙酰基-D-扁桃酸、乙酰氧基乙酸中的一种或几种。
优选的，所述功能聚合物为耐高电压、线性可溶解且与电解液亲和性强的聚合物。该功能聚合物为可溶性聚腈类(优选聚丙烯腈、芳腈基聚合物、腈类共聚物)、可溶性聚烯烃(优选聚对苯撑乙烯、聚苯乙烯、烯烃共聚物)、可溶性聚酯(优选聚甲基丙烯酸甲酯、聚丙烯酸甲酯、酯类共聚物、聚硼酸酯、聚碳酸酯)、可溶性含氟聚合物(优选聚四氟乙烯、聚偏氟乙烯、聚偏氟乙烯-六氟丙烯)、可溶性有机硅聚合物、可溶性聚苯硫醚、可溶性砜聚合物中的一种或多种组合。
优选的，在步骤(2)中，所述锂盐在所述混合液中的浓度为0.2mol/L-3mol/L；所述锂盐含有氟元素、氧元素、氯元素、砷元素、硼元素、硫元素、磷元素、氮元素、碳元素中的一种或几种。
在本发明的一些具体实施例中，锂盐优选为高氯酸锂(LiClO4)、六氟磷酸锂(LiPF6)、六氟砷酸锂(LiAsF6)、四氟硼酸锂(LiBF4)、双草酸硼酸锂(LiBOB)、草酸二氟硼酸锂(LiDFOB)、双二氟磺酰亚胺锂(LiFSI)、双三氟甲基磺酰亚胺锂(LiTFSI)、三氟甲基磺酸锂(LiCF3SO3)、双丙二酸硼酸(LiBMB)、丙二酸草酸硼酸锂(LiMOB)、六氟锑酸锂(LiSbF6)、二氟磷酸锂(LiPF2O2)、4,5-二氰基-2-三氟甲基咪唑锂(LiDTI)、二(三氟甲基磺酰)亚胺锂(LiN(SO2CF3)2)、LiN(SO2C2F5)2、LiC(SO2CF3)3和LiN(SO2F)2中的一种或几种。
其中羟基氟结构类添加剂结构式为
R13为有机官能团，R13可以单独或互相结合形成环状结构且R13中至少含有一个羟基；优选的，所述羟基氟结构类添加剂为羟基氟他胺、8-氟-4-羟基喹啉、5-氟间苯二酚、2-氟-6-羟基苯甲腈、3-氟-2-羟基吡啶、对三氟甲基苯酚、4-氟-4'-羟基联苯、3-氟-5-羟基吡啶、2-氟-3-羟基吡啶、2-氟-5-羟基吡啶、2-氟-4-羟基苯腈、3-氟-4-羟基苯腈、5-氟-8-羟基喹啉、5-氟-4-羟基嘧啶、7-氟-4-羟基喹啉、2-羟基-5-氟吡啶、4-羟基-6-氟喹啉、2-氟-6-羟基吡啶、7-氟-8-羟基喹啉、2-羟基-5-氟嘧啶、4-氟-3-羟基苯腈、8-氟-4-羟基喹啉、3-三氟甲基苯酚、4-氟-2-羟基吡啶、3-氟-5-羟基苯甲腈、3-氟-4-(羟基甲基)苯酚、对三氟甲基苯酚、2-氟-5-三氟甲基苯酚中的一种或几种。
其中羧基氟结构类添加剂结构式为
R14为有机官能团，R14可以单独或互相结合形成环状结构且R14中至少含有一个羧基；优选的，所述羧基氟结构类添加剂为2-氟对苯二甲酸、5-氟-2-羧基吡啶、4-氰基-2-氟苯酸、5-氟烟酸、4-氟-1H-吲哚-7-羧酸、4-羧基-3-氟苯硼酸、(3-氟苯基)环丙基羧酸、(2-氟苯基)环丙基羧酸、1-(4-氟苯基)环丙烷甲酸、3-羧基-5-氟苯基硼酸、2-羧基-5-氟苯基硼酸、2-(三氟甲基)嘧啶-5-羧酸、2-氟-4-甲基吡啶-5-羧酸、4-三氟甲基喹啉-2-甲酸、3-(三氟甲基)喹啉-8-羧酸、4-羟基-6-氟喹啉-3-甲酸、5-三氟甲基吡啶-2-羧酸、3-三氟甲基吡啶-2-羧酸、4-氨基-3-氟苯羧酸甲酯、2-三氟甲基喹啉-4-羧酸、6-(三氟甲基)吲哚-2-羧酸、5-氨基-2-氟-4-吡啶羧酸、2-羧基-4-氟苯硼酸、1-(三氟甲基)环戊烷羧酸、5-羧基-2-氟苯硼酸中的一种或几种；
其中羧基氟结构类添加剂结构式为
R20为有机官能团，R20可以单独或互相结合形成环状结构且R20中至少含有一个羧基，优选的，所述羧基氟结构类添加剂为2-氟对苯二甲酸、5-氟-2-羧基吡啶、4-氰基-2-氟苯酸、5-氟烟酸、4-氟-1H-吲哚-7-羧酸、4-羧基-3-氟苯硼酸、(3-氟苯基)环丙基羧酸、(2-氟苯基)环丙基羧酸、1-(4-氟苯基)环丙烷甲酸、3-羧基-5-氟苯基硼酸、2-羧基-5-氟苯基硼酸、2-(三氟甲基)嘧啶-5-羧酸、2-氟-4-甲基吡啶-5-羧酸、4-三氟甲基喹啉-2-甲酸、3-(三氟甲基)喹啉-8-羧酸、4-羟基-6-氟喹啉-3-甲酸、5-三氟甲基吡啶-2-羧酸、3-三氟甲基吡啶-2-羧酸、4-氨基-3-氟苯羧酸甲酯、2-三氟甲基喹啉-4-羧酸、6-(三氟甲基)吲哚-2-羧酸、5-氨基-2-氟-4-吡啶羧酸、2-羧基-4-氟苯硼酸、1-(三氟甲基)环戊烷羧酸、5-羧基-2-氟苯硼酸中的一种或几种。
优选的，所述功能反应剂为可与羟基或羧基反应的试剂或低聚物。功能反应剂在电解质中含量为0.01％～10％；
羟基功能反应剂结构为
其中羟基功能反应剂结构为含至少两个异氰酸酯官能团、醛官能团的试剂或聚合物，优选异佛尔酮二异氰酸酯、1,3-双(1-异氰酸根-1-甲基乙基)苯、对苯二异氰酸酯、萘二异氰酸酯、间苯二异氰酸酯、邻苯二甲基二异氰酸酯、二甲基联苯二异氰酸酯、间苯二甲基异氰酸酯、反-1,4-环己基二异氰酸酯、环己烷-1,4-二异氰酸酯、2,5-二异氰酸甲苯酯、聚六亚甲基二异氰酸酯、2,4-甲苯二异氰酸酯、3,3'-二氯联苯-4,4'-二异氰酸酯、4-氯-6-甲基间苯基二异氰酸酯、4,4-二异氰酸酯二环己基甲烷、十二烷基苯-2,4-二异氰酸酯、三苯基甲烷三异氰酸酯、L-赖氨酸三异氰酸酯、三(对异氰酸酯基苯)胺、硫代磷酸三(4-苯基异氰酸酯)；
羧基功能反应剂结构为
R21-N＝C＝N-R22其中羧基功能反应剂结构为含至少两个氮丙啶官能团、聚碳化二亚胺能团的试剂或聚合物，优选三羟甲基丙烷三(3-吖丙啶基丙酸酯)、N,N-六亚甲基-1,6-二(1-氮丙啶酰胺)、1,1’-(1,3-苯二甲酰)双(2-甲基-氮丙啶)、唾替派、季戊四醇三(3-氮丙啶基)丙酸酯、三羟甲基丙烷三(2-甲基-1-氮杂环丙烷丙酸酯)、脂肪族聚碳化二亚胺、芳族聚碳化二亚胺中的一种或几种。
本发明第三个方面公开了上述方法得到的聚合物电解质。
本发明第四个方面公开了一种锂离子电池，包括上述的聚合物电解质。
本发明第五个方面公开了一种锂离子电池的制备方法，包括：
S1：按重量份数计，将5～90份有机溶剂溶解0.01～27份功能聚合物制备均匀混合A体系；
S2：将A体系、锂盐、功能添加剂和功能反应剂混合均匀，即得到混合液；
S3：将所述混合液加入电池电芯中，热压处理后进行原位聚合粘结得到锂离子电池。
优选的，在S3中，将S2中所述混合液在注液到电池电芯中，混合液充分浸渍正极极片、中间隔离层和负极极片，并填充于其空隙位置及正负极之间的位置，进行封装后，热压化成进行原位聚合后，进行再次封装抽气，得到半固态锂离子电池。
更优选的，在S3中所述正极极片中正极活性物质含有锂元素、铁元素、磷元素、钴元素、锰元素、镍元素、铝元素中的一种或几种，其中正极活性物质经过铝镁、钛、锆、镍、锰、钇、镧、锶等中的一种或几种掺杂包覆元素。所述正极活性物质优选为磷酸铁锂、钴酸锂、镍钴锰三元电池材料、锰酸锂、镍钴铝三元电池材料、富锂锰基材料中的一种或几种。
更优选的，在S3中所述中间隔离层厚度为3um～100um，中间隔离层为高分子材料隔膜、氧化物电解质、聚合物电解质、硫化物电解质、陶瓷颗粒、聚合物微球中的一种或几种。
更优选的，在S3中所述负极极片活性物质为碳材料、金属铋、锂金属、氮化物、镁基合金、铟基合金、硼基材料、硅基材料、锡基材料、锑基合金、镓基合金、锗基合金、铝基合金、铅基合金、锌基合金、钛的氧化物、纳米过渡金属氧化物MO、铁的氧化物、铬的氧化物、钼的氧化物、磷化物中的一种或多种的组合，其中M为Co、Ni、Cu或Fe中的一种或几种。
更优选的，在S3中所述电解质在电池中热压化成进行原位聚合后，得到半固态或固态锂离子电池，其中聚合物电解质完全区别于液体电解质，具有半固态或固态聚合物电解质性质，其平均分子量为1500～30W区间范围。
在符合本领域常识的基础上，上述各优选条件，可任意组合，而不超出本发明的构思与保护范围。
本发明区别于传统的全固态电池和半固态凝胶电解质，主要采用含羧基或羟基的溶剂、能与羧基或羟基发生交联的试剂及筛选少量有机溶剂溶解锂盐，将封装好的锂离子电池电芯进行注液，注液后混合液充分浸润正负极极片后，进行高温原位固态化反应，制备界面接触良好的原位半固态或固态锂离子电池。
本发明中主要以含羧基或羟基的氟结构、含羧基或羟基的碳酸酯结构、含羧基或羟基的酯结构为单体，以少量该类有机溶剂溶解锂盐，并加入能与羧基或羟基发生交联的试剂，在一定温度下进行交联反应，制备原位半固态或固态锂离子电池。
与现有技术相比，本发明具有以下有益效果：1、本发明中氟结构、碳酸酯结构等以梳状链接在聚合物中，该类氟结构键能高，能够改善聚合物电解质的电化学稳定性，提升高能量密度的电池性能；2、本发明中，聚合物电解质单体为含羧基或羟基的氟结构、酯结构、碳酸酯结构，采用能与羟基或羧酸反应的交联剂，该类交联剂能有效与羟基或羧基反应且在后续锂离子电池高温处理时，交联剂会热分解，与其他制备方式相比，能够有效减少电池循环过程中副反应的产生；3、本发明聚合物电解质与正负极浸润性好，主要是采用原位聚合方式，在正负极极片内部形成完整锂离子导通通道，提升高能量密度锂离子电池的性能。
与此同时，在本发明中通过设计含羧基或羟基的氟结构单体、含羧基或羟基的碳酸酯结构单体、含羧基或羟基的酯结构单体的单体、锂盐种类、锂盐浓度、交联剂、反应条件等，制备结构可控的高能量密度的锂离子电池。该高能量密度的锂离子电池基于现有锂离子电池加工工艺，具有良好的加工性能和电化学性能，具有一定的应用前景。
具体实施方式
下面结合实施例对本发明的技术方案进行详细描述，但并不因此将本发明限制在所述的实施例范围之中。
下述说明中所使用到的试剂、材料以及仪器如没有特殊的说明，均为常规试剂、常规材料以及常规仪器，均可商购获得，所涉及的试剂也可通过常规合成方法合成获得。
实施例1
为了实现上述一种聚合物电解质的制备方法及其含该结构的锂离子电池目的，本发明采取如下的技术解决方案：
S1：按重量份数计，将0.3份过氧化二碳酸二-3-甲氧丁酯、0.4份(S)-4-(甲氧甲基)-1,3-二氧杂环戊烷-2-酮、0.2份异丁基羰基乳糖酸酐、0.7份乳酸碳酸乙酯、0.1份2-羟基苯乙酸甲酯、0.3份羟基三甲基乙酸甲酯、0.3份3-羟基己酸甲酯、0.5份3-羟基己酸乙酯、0.2份2-羧基苯基硼酸频哪醇酯、0.5份4,5-二羧基-十五内酯、0.3份4-羧基苯乙酸甲酯、0.2份1,1-环丙基二甲酸单甲酯溶解0.01份聚甲基丙烯酸甲酯、聚丙烯酸甲酯、聚硼酸酯和聚碳酸酯(聚甲基丙烯酸甲酯、聚丙烯酸甲酯、聚硼酸酯和聚碳酸酯质量比为1:1:2:1)，混合均匀后得到A体系；
S2：将A体系、锂盐、功能添加剂、功能反应剂均匀混合，得到混合液。其中锂盐为质量比为1:5:1的高氯酸锂(LiClO4)、六氟磷酸锂(LiPF6)和六氟砷酸锂(LiAsF6)，该混合液中锂盐浓度为3mol/L；功能添加剂为3-氟-4-羟基苯腈占总质量2.8％、5-氟-8-羟基喹啉占总质量3.5％、5-氟-4-羟基嘧啶占总质量3.50％、7-氟-4-羟基喹啉占总质量2.20％、3-羧基-5-氟苯基硼酸占总质量2.3％、2-羧基-5-氟苯基硼酸占总质量3.10％、2-(三氟甲基)嘧啶-5-羧酸占总质量2.60％，功能添加剂占总质量的20％；功能反应剂为异佛尔酮二异氰酸酯占总质量2.00％、1,3-双(1-异氰酸根-1-甲基乙基)苯占总质量2.00％、三羟甲基丙烷三(3-吖丙啶基丙酸酯)占总质量1.00％、N,N-六亚甲基-1,6-二(1-氮丙啶酰胺)占总质量5.0％，功能反应剂占总质量的10％；
S3：将S2中所述混合液在注液到电池电芯中，混合液充分浸渍正极极片、中间隔离层和负极极片，并填充于其空隙位置及正负极之间的位置，进行封装后，热压化成进行原位聚合后，进行再次封装抽气，得到锂离子电池。
实施例2
本实施例也公开了一种锂离子电池的制备方法，具体方法参见实施例1中S1-S3，与实施例1的唯一区别在于S1-S3过程中有机溶剂、功能聚合物、锂盐、功能添加剂、功能反应剂的比例及种类不同，具体信息参见下表1、表2和表3。
实施例3
本实施例也公开了一种锂离子电池的制备方法，具体方法参见实施例1中S1-S3，与实施例1的唯一区别在于S1-S3过程中有机溶剂、功能聚合物、锂盐、功能添加剂、功能反应剂的比例及种类不同，具体信息参见下表1、表2和表3。
实施例4
本实施例也公开了一种锂离子电池的制备方法，具体方法参见实施例1中S1-S3，与实施例1的唯一区别在于S1-S3过程中有机溶剂、功能聚合物、锂盐、功能添加剂、功能反应剂的比例及种类不同，具体信息参见下表1、表2和表3。
实施例5
本实施例也公开了一种锂离子电池的制备方法，具体方法参见实施例1中S1-S3，与实施例1的唯一区别在于S1-S3过程中有机溶剂、功能聚合物、锂盐、功能添加剂、功能反应剂的比例及种类不同，具体信息参见下表1、表2和表3。
实施例6
本实施例也公开了一种锂离子电池的制备方法，具体方法参见实施例1中S1-S3，与实施例1的唯一区别在于S1-S3过程中有机溶剂、功能聚合物、锂盐、功能添加剂、功能反应剂的比例及种类不同，具体信息参见下表1、表2和表3。
对比例1
对比例1制备具体方法参见实施例6中S1-S3，与实施例6的唯一区别在于S1-S3过程中，对比例1无功能添加剂，其他条件与实施例6一致，具体信息参见下表1、表2和表3。
将正极片、隔离膜、负极片按顺序组装好，将上述制备好的电解液注入到干燥后的电池中，经封装、静置、化成等工序，得到对比例1的锂离子电池。
表1
表2
表3
实验数据：
1、测试各个实施例的电解质电导率性能，结果如表4所示。
表4
| 样品编号 | 电导率/(mS/cm) |
| 实施例1 | 4.75 |
| 实施例2 | 4.62 |
| 实施例3 | 4.53 |
| 实施例4 | 4.47 |
| 实施例5 | 4.85 |
| 实施例6 | 4.32 |
| 对比例1 | 3.16 |
本发明实施例电导率范围为4.32～4.85mS/cm之间，对比例电导率为3.16mS/cm。本发明实施例1-6的聚合物电解质电导率略高于对比例1，说明本发明专利中的含氟添加剂能促进锂离子解离，提升聚合物电解质电导率。
2、锂离子电池充放电；
将实施例1-6、对比例1制备的锂离子电池进行充放电循环测试，结果如表5所示，测试条件为25℃、50％湿度、1C/1C充放电、电压2.75V-4.2V。
表5
从表可以看出：本发明专利公开的实施例1-6方法制备得到的锂离子电池与对比例1制备的锂离子电池性能相比，本发明专利实施例1-6方案制备的锂离子电池性能更优。主要原因是本发明专利方案中采用了含氟结构添加剂，该含氟结构添加剂能够改善聚合物电解质的电化学稳定性，提升电池的循环寿命。
上述实施例为本发明较佳的实施方式，但本发明的实施方式并不受上述实施例的限制，其他的任何未背离本发明的精神实质与原理下所作的改变、修饰、替代、组合、简化，均应为等效的置换方式，都包含在本发明的保护范围之内。
Claims (10)
1.一种聚合物电解质，其特征在于，所述聚合物电解质包括氟结构：
所述R52-R60均为有机官能团，所述氟结构的分子量为500～10W。
2.根据权利要求1所述的聚合物电解质，其特征在于，所述聚合物电解质还包括碳酸酯结构；其中所述碳酸酯结构为：
所述R32-R40均为有机官能团，所述碳酸酯结构的分子量为500～10W。
3.根据权利要求1所述的聚合物电解质，其特征在于，所述聚合物电解质还包括下式酯结构中的一种；
所述R32-R39、R44-R51均为有机官能团，所述酯结构的分子量为500～10W。
4.一种聚合物电解质的制备方法，其特征在于，包括：
(1)按重量份数计，将5～90份有机溶剂溶解0.01～27份功能聚合物制备均匀混合A体系；
(2)将A体系、锂盐、功能添加剂和功能反应剂混合均匀，即得到混合液；
(3)将所述混合液进行原位聚合得到聚合物电解质。
5.根据权利要求4所述的方法，其特征在于，所述有机溶剂为羟基碳酸酯、羧基碳酸酯、羟基酯或羧基酯。
6.根据权利要求5所述的方法，其特征在于，所述羟基碳酸酯结构为
R1和R2为有机官能团，R1和R2可以单独或互相结合形成环状结构；所述羧基碳酸酯结构为
R3和R4为有机官能团，R3和R4可以单独或互相结合形成环状结构；所述羟基酯结构为
R5、R6、R7和R8为有机官能团，R5、R6、R7和R8可以单独或互相结合形成环状结构；所述羧基酯结构为
R9、R10、R11和R12为有机官能团，R9、R10、R11和R12可以单独或互相结合形成环状结构。
7.根据权利要求4所述的方法，其特征在于，所述功能添加剂为羟基氟结构类添加剂、羧基氟结构类添加剂中的一种或多种。
8.根据权利要求7所述的方法，其特征在于，其中羟基氟结构类添加剂结构式为
R13为有机官能团，R13可以单独或互相结合形成环状结构且R13中至少含有一个羟基；优选的，所述羟基氟结构类添加剂为羟基氟他胺、8-氟-4-羟基喹啉、5-氟间苯二酚、2-氟-6-羟基苯甲腈、3-氟-2-羟基吡啶、对三氟甲基苯酚、4-氟-4'-羟基联苯、3-氟-5-羟基吡啶、2-氟-3-羟基吡啶、2-氟-5-羟基吡啶、2-氟-4-羟基苯腈、3-氟-4-羟基苯腈、5-氟-8-羟基喹啉、5-氟-4-羟基嘧啶、7-氟-4-羟基喹啉、2-羟基-5-氟吡啶、4-羟基-6-氟喹啉、2-氟-6-羟基吡啶、7-氟-8-羟基喹啉、2-羟基-5-氟嘧啶、4-氟-3-羟基苯腈、8-氟-4-羟基喹啉、3-三氟甲基苯酚、4-氟-2-羟基吡啶、3-氟-5-羟基苯甲腈、3-氟-4-(羟基甲基)苯酚、对三氟甲基苯酚、2-氟-5-三氟甲基苯酚中的一种或几种；
其中羧基氟结构类添加剂结构式为
R20为有机官能团，R20可以单独或互相结合形成环状结构且R20中至少含有一个羧基，优选的，所述羧基氟结构类添加剂为2-氟对苯二甲酸、5-氟-2-羧基吡啶、4-氰基-2-氟苯酸、5-氟烟酸、4-氟-1H-吲哚-7-羧酸、4-羧基-3-氟苯硼酸、(3-氟苯基)环丙基羧酸、(2-氟苯基)环丙基羧酸、1-(4-氟苯基)环丙烷甲酸、3-羧基-5-氟苯基硼酸、2-羧基-5-氟苯基硼酸、2-(三氟甲基)嘧啶-5-羧酸、2-氟-4-甲基吡啶-5-羧酸、4-三氟甲基喹啉-2-甲酸、3-(三氟甲基)喹啉-8-羧酸、4-羟基-6-氟喹啉-3-甲酸、5-三氟甲基吡啶-2-羧酸、3-三氟甲基吡啶-2-羧酸、4-氨基-3-氟苯羧酸甲酯、2-三氟甲基喹啉-4-羧酸、6-(三氟甲基)吲哚-2-羧酸、5-氨基-2-氟-4-吡啶羧酸、2-羧基-4-氟苯硼酸、1-(三氟甲基)环戊烷羧酸、5-羧基-2-氟苯硼酸中的一种或几种。
9.根据权利要求4所述的方法，其特征在于，所述功能反应剂为可与羟基或羧基反应的试剂或低聚物。
10.一种锂离子电池，其特征在于，包括权利要求1-3所述的聚合物电解质，或者包括根据权利要求4-9所述方法制备得到的聚合物电解质。
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