CN103700883B - 一种提高锂电池高电压性能的电解液 - Google Patents
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- 239000003792 electrolyte Substances 0.000 title claims abstract description 31
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 27
- 239000000654 additive Substances 0.000 claims abstract description 15
- 230000000996 additive effect Effects 0.000 claims abstract description 15
- 150000004649 carbonic acid derivatives Chemical class 0.000 claims abstract description 11
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000013538 functional additive Substances 0.000 claims abstract description 8
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 8
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 8
- 239000003960 organic solvent Substances 0.000 claims abstract description 5
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 9
- YTZKOQUCBOVLHL-UHFFFAOYSA-N tert-butylbenzene Chemical compound CC(C)(C)C1=CC=CC=C1 YTZKOQUCBOVLHL-UHFFFAOYSA-N 0.000 claims description 8
- 239000008151 electrolyte solution Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- ZZXUZKXVROWEIF-UHFFFAOYSA-N 1,2-butylene carbonate Chemical compound CCC1COC(=O)O1 ZZXUZKXVROWEIF-UHFFFAOYSA-N 0.000 claims description 4
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 claims description 4
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 claims description 4
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 4
- BJWMSGRKJIOCNR-UHFFFAOYSA-N 4-ethenyl-1,3-dioxolan-2-one Chemical compound C=CC1COC(=O)O1 BJWMSGRKJIOCNR-UHFFFAOYSA-N 0.000 claims description 4
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 4
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- 235000010290 biphenyl Nutrition 0.000 claims description 4
- 239000004305 biphenyl Substances 0.000 claims description 4
- HHNHBFLGXIUXCM-GFCCVEGCSA-N cyclohexylbenzene Chemical compound [CH]1CCCC[C@@H]1C1=CC=CC=C1 HHNHBFLGXIUXCM-GFCCVEGCSA-N 0.000 claims description 4
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 claims description 4
- NKDDWNXOKDWJAK-UHFFFAOYSA-N dimethoxymethane Chemical compound COCOC NKDDWNXOKDWJAK-UHFFFAOYSA-N 0.000 claims description 4
- VUPKGFBOKBGHFZ-UHFFFAOYSA-N dipropyl carbonate Chemical compound CCCOC(=O)OCCC VUPKGFBOKBGHFZ-UHFFFAOYSA-N 0.000 claims description 4
- QHTJSSMHBLGUHV-UHFFFAOYSA-N 2-methylbutan-2-ylbenzene Chemical compound CCC(C)(C)C1=CC=CC=C1 QHTJSSMHBLGUHV-UHFFFAOYSA-N 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 229910015015 LiAsF 6 Inorganic materials 0.000 claims description 2
- 229910013063 LiBF 4 Inorganic materials 0.000 claims description 2
- 229910013684 LiClO 4 Inorganic materials 0.000 claims description 2
- 229910013872 LiPF Inorganic materials 0.000 claims description 2
- 229910013870 LiPF 6 Inorganic materials 0.000 claims description 2
- 101150058243 Lipf gene Proteins 0.000 claims description 2
- 125000001931 aliphatic group Chemical group 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims description 2
- 150000004651 carbonic acid esters Chemical class 0.000 claims description 2
- SIXOAUAWLZKQKX-UHFFFAOYSA-N carbonic acid;prop-1-ene Chemical compound CC=C.OC(O)=O SIXOAUAWLZKQKX-UHFFFAOYSA-N 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 2
- -1 methyl ethyl Chemical group 0.000 claims description 2
- 150000007984 tetrahydrofuranes Chemical group 0.000 claims description 2
- 230000001629 suppression Effects 0.000 abstract description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 10
- 229910001416 lithium ion Inorganic materials 0.000 description 10
- 125000003545 alkoxy group Chemical group 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 125000001188 haloalkyl group Chemical group 0.000 description 2
- 125000001475 halogen functional group Chemical group 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 229910011281 LiCoPO 4 Inorganic materials 0.000 description 1
- 229910013246 LiNiMnO Inorganic materials 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 230000010261 cell growth Effects 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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- 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
- H01M10/0566—Liquid materials
- H01M10/0567—Liquid materials characterised by the additives
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- H—ELECTRICITY
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- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
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- 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
- H01M2300/0025—Organic electrolyte
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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
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Abstract
本发明提供一种提高锂电池高电压性能的电解液，该电解液由四类组份组成：锂盐，碳酸酯类和/或醚类有机溶剂，高电压添加剂和其他功能添加剂；其中锂盐和高电压添加剂组分在此电解液中的摩尔浓度范围均是：0.001～2mol/L，其他功能添加剂组分的摩尔浓度范围是：0～0.5mol/L。本发明通过在锂电池电解液中添加高电压添加剂，提升电解液在高电压下的稳定性，有利于提高锂电池的高电压循环寿命以及抑制锂电池膨胀。
Description
技术领域
本发明属于化学材料技术领域，具体涉及一种提高锂电池高电压性能的电解液。
背景技术
随着锂离子电池市场化的不断深入，人们对锂离子电池的期望越来越高。目前商品化的锂离子电池已经很难满足实际应用的需要，如移动电话，摄像机，笔记本电脑等便携式设备。随着在电动汽车，无绳电动工具及军事上的应用，对锂离子电池的能量密度提出了更高的要求，而LiNiMnO4、LiNiCoMnO2和LiCoPO4能够在较高的电压（大于4.2V）下发生锂离子的脱嵌反应，因此为提高锂离子电池的能量密度带来了新希望。但是锂离子电池的电解液在高电压下容易分解，导致锂离子电池的充放电效率比较低，循环性能比较差，制约了高电压锂离子电池的进一步发展。
为了解决这个问题，提出使用氟代溶剂，如FEC的方案。然而，大量的氟代溶剂虽然解决了电解液耐电压的问题，但是电解液电导率降低，而且SEI膜的电阻进一步增大，充放电性能降低，同时气体产生十分显著，电池膨胀较大。因此开发耐高压的电解质材料成为国内外众多研究者努力的目标。
发明内容
基于以上技术背景，本发明的目的在于提供一种提高锂电池高电压性能的电解液，通过在锂电池电解液中添加高电压添加剂，提高电解液的高电压性能，有利于提高锂电池的高电压循环寿命以及抑制锂电池膨胀。
本发明的方案是通过如下技术措施来实现的：
一种提高锂电池高电压性能的电解液，其特点在于该电解液由以下四类组份组成：（A）锂盐、（B）碳酸酯类和/或醚类有机溶剂、（C）高电压添加剂和（D）其他功能添加剂；其中（A）锂盐和（C）高电压添加剂组分在此电解液中所占的摩尔浓度范围均是：0.001～2mol/L，（D）其他功能添加剂组分在此电解液中所占的摩尔浓度范围均是：0～0.5mol/L，所述(C)高电压添加剂具有下面结构特点：
。
其中R1为选自卤素、卤代烷基、卤代烷氧基、卤代烯烃基、卤代苯基或卤代联苯基，其中：卤素为F、Cl或Br，卤代包含部分取代和全取代，R2选自烷基、烷氧基、卤代烷基、卤代烷氧基。
以上所述高电压添加剂结构中的卤素为F、Cl、Br中的至少一种，卤代包含部分取代和全取代。
以上所述高电压添加剂结构中的R1和R2优选为R1=F，R2=CH2，FC6H4C3H5；R1=F，R2=C2H4，FC6H4C4H7；R1=CH2F，R2=CH2，CH2FC6H4C3H5；R1=CH2F，R2=C2H4，CH2FC6H4C4H7；R1=F，R2=CF2，FC6H4C3F2H3；R1=F，R2=C2F4，FC6H4C4F4H3。
以上所述（A）锂盐选自LiBF4，LiPF6，LiAsF6，LiClO4，LiPFb[(C6Fs(CpFqH(2p+1-q))tH(5-s-t))](6-b)，b=0，1，2，3，4，5；s=0，1，2，3，4，5；t=0，1，2，3，4，5；p，q为大于等于零的整数中的至少一种。
以上所述（B）碳酸酯类为环状的碳酸酯类和/或链状碳酸酯类化合物；环状的碳酸酯类化合物选自碳酸乙烯酯（EC）、碳酸丙烯酯（PC）、γ-丁内酯（GBL）和碳酸亚丁酯（BC）中的一种或一种以上组合物；所述的链状碳酸酯类化合物选自碳酸二甲酯（DMC）、碳酸二乙酯（DEC）、碳酸二丙酯（DPC）、碳酸甲基乙基酯（EMC）、碳数为3～8个的直链或支链脂肪单醇与碳酸合成的碳酸酯衍生物中的一种或一种以上组合物；所述的醚类有机溶剂选自四氢呋喃（THF）、2-甲基四氢呋喃（2-Methyl-THF）、1，3-二氧环戊烷（DOL）、二甲氧甲烷（DMM）、1，2-二甲氧乙烷（DME）和二甘醇二甲醚（dimethylcarbitol）中的至少一种。
以上所述（D）其他功能添加剂为联苯（BP），碳酸亚乙烯酯（VC），碳酸乙烯亚乙酯（VEC），环己基苯（CHB），叔丁基苯（TBB），叔戊基苯（TPB）中的至少一种。
本发明电解质溶液可应用于一次电池、二次电池以及锂离子电池。
本发明提供了一种提高锂电池高电压性能的电解液，该电解质溶液通过在锂电池电解液中添加高电压添加剂，能大大提高电解液的高电压性能，有利于提高锂电池的高电压循环寿命以及抑制锂电池膨胀，具有较好的推广应用价值。
具体实施方式
为了使本发明的目的、技术方案及优点更加清楚明白，本发明用以下具体实施例进行说明，但本发明绝非仅限于这些例子。
本发明以表格的形式例举了1～84种基于含双硼亚胺锂的电解质溶液的成份组成、以及各电解质溶液的电池容量百分比的测试数据，详见下表：
由上述实施例可见，该电解质溶液中没有添加高电压添加剂时，周容量百分率较低（实施例1-10），添加后周容量百分率大幅提高（实施例11-84）通过在锂电池电解液中添加高电压添加剂，大大提高了电解液的高电压性能，有利于提高锂电池的高电压循环寿命以及抑制锂电池膨胀，具有较好的市场推广应用价值。
Claims (5)
1.一种提高锂电池高电压性能的电解液，其特征在于：该电解液由以下四类组份组成：（A）锂盐、（B）碳酸酯类和/或醚类有机溶剂、（C）高电压添加剂和（D）其他功能添加剂；其中（A）锂盐和（C）高电压添加剂组分在此电解液中所占的摩尔浓度范围均是：0.001～2mol/L，（D）其他功能添加剂组分在此电解液中所占的摩尔浓度范围均是：0～0.5mol/L，所述(C)高电压添加剂具有下面结构特点：
，
其中R1=F，R2=FC6H4C3H5；R1=F，R2=FC6H4C4H7；R1=CH2F，R2=CH2FC6H4C3H5；R1=CH2F，R2=CH2FC6H4C4H7；R1=F，R2=FC6H4C3F2H3；R1=F，R2=FC6H4C4F4H3。
2.根据权利要求1所述的一种提高锂电池高电压性能的电解液，其特征在于：所述（A）锂盐选自LiBF4，LiPF6，LiAsF6，LiClO4，LiPFb[(C6Fs(CpFqH(2p+1-q))tH(5-s-t))](6-b)，b=0，1，2，3，4，5；s=0，1，2，3，4，5；t=0，1，2，3，4，5；p，q为大于等于零的整数中的至少一种。
3.根据权利要求1所述的一种提高锂电池高电压性能的电解液，其特征在于：所述（B）碳酸酯类为环状的碳酸酯类和/或链状碳酸酯类化合物；环状的碳酸酯类化合物选自碳酸乙烯酯（EC）、碳酸丙烯酯（PC）、γ-丁内酯（GBL）和碳酸亚丁酯（BC）中的一种或一种以上组合物；所述的链状碳酸酯类化合物选自碳酸二甲酯（DMC）、碳酸二乙酯（DEC）、碳酸二丙酯（DPC）、碳酸甲基乙基酯（EMC）、碳数为3～8个的直链或支链脂肪单醇与碳酸合成的碳酸酯衍生物中的一种或一种以上组合物；所述的醚类有机溶剂选自四氢呋喃（THF）、2-甲基四氢呋喃（2-Methyl-THF）、1，3-二氧环戊烷（DOL）、二甲氧甲烷（DMM）、1，2-二甲氧乙烷（DME）和二甘醇二甲醚（dimethylcarbitol）中的至少一种。
4.根据权利要求1所述的一种提高锂电池高电压性能的电解液，其特征在于：所述（D）其他功能添加剂为联苯（BP），碳酸亚乙烯酯（VC），碳酸乙烯亚乙酯（VEC），环己基苯（CHB），叔丁基苯（TBB），叔戊基苯（TPB）中的至少一种。
5.根据权利要求1所述的一种提高锂电池高电压性能的电解液，其特征在于：该电解质溶液可应用于锂一次电池、锂二次电池。
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