CN108258305B - 电解质与电池 - Google Patents
电解质与电池 Download PDFInfo
- Publication number
- CN108258305B CN108258305B CN201711323966.9A CN201711323966A CN108258305B CN 108258305 B CN108258305 B CN 108258305B CN 201711323966 A CN201711323966 A CN 201711323966A CN 108258305 B CN108258305 B CN 108258305B
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- Prior art keywords
- electrolyte
- oxide
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- lithium
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- 230000001070 adhesive effect Effects 0.000 claims abstract description 9
- 229920000642 polymer Polymers 0.000 claims description 27
- 239000002243 precursor Substances 0.000 claims description 11
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- ZUHZGEOKBKGPSW-UHFFFAOYSA-N tetraglyme Chemical compound COCCOCCOCCOCCOC ZUHZGEOKBKGPSW-UHFFFAOYSA-N 0.000 claims description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 6
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- 229910000552 LiCF3SO3 Inorganic materials 0.000 claims description 3
- 229910010937 LiGaCl4 Inorganic materials 0.000 claims description 3
- 229910013406 LiN(SO2CF3)2 Inorganic materials 0.000 claims description 3
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- 238000004132 cross linking Methods 0.000 claims description 3
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- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 claims description 3
- 229910001486 lithium perchlorate Inorganic materials 0.000 claims description 3
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- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims description 3
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 claims description 3
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- CVJYOKLQNGVTIS-UHFFFAOYSA-K aluminum;lithium;titanium(4+);phosphate Chemical compound [Li+].[Al+3].[Ti+4].[O-]P([O-])([O-])=O CVJYOKLQNGVTIS-UHFFFAOYSA-K 0.000 claims description 2
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- CEMTZIYRXLSOGI-UHFFFAOYSA-N lithium lanthanum(3+) oxygen(2-) titanium(4+) Chemical compound [Li+].[O--].[O--].[O--].[O--].[Ti+4].[La+3] CEMTZIYRXLSOGI-UHFFFAOYSA-N 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
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- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 239000011255 nonaqueous electrolyte Substances 0.000 description 1
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Images
Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F7/00—Compounds of aluminium
- C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/002—Compounds containing, besides titanium, two or more other elements, with the exception of oxygen or hydrogen
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- C—CHEMISTRY; METALLURGY
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Abstract
电解质包括:(a)100重量份的氧化系固态无机电解质;(b)20至70重量份的[Li(‑OR1)n‑OR2]Y,其中R1为C1‑4的烷撑基,R2为C1‑4的烷基,n介于2至100之间,且Y为PF6 ‑、BF4 ‑、AsF6 ‑、SbF6 ‑、ClO4 ‑、AlCl4 ‑、GaCl4 ‑、NO3 ‑、C(SO2CF3)3 ‑、N(SO2CF3)2 ‑、SCN‑、CF3CF2SO3 ‑、C6F5SO3 ‑、CF3CO2 ‑、SO3F‑、B(C6H5)4 ‑、CF3SO3 ‑、或上述的组合;(c)1至10重量份的纳米氧化物;以及(d)1至20重量份的黏着剂。上述电解质可置于正极与负极之间以形成电池。
Description
技术领域
本发明关于电池与其采用的电解质。
背景技术
现行液态锂离子电池的重量能量密度偏低,循环寿命有限,导致单位蓄电成本居高不下。但是单方面提升电池的能量密度,容易加速诱发电化学电池一连串安全问题,其中包含漏液、膨罐、发热、冒烟、燃烧、或爆炸等问题,严重限制使用性。综上所述,目前亟需新的电解质解决上述问题,同时达到能量、寿命、成本、与安全等因素的最佳平衡。
发明内容
本公开一实施例提供的电解质,包括:(a)100重量份的氧化系固态无机电解质;(b)20至70重量份的[Li(-OR1)n-OR2]Y,其中R1为C1-4的烷撑基,R2为C1-4的烷基,n介于2至100之间,且Y为PF6 -、BF4 -、AsF6 -、SbF6 -、ClO4 -、AlCl4 -、GaCl4 -、NO3 -、C(SO2CF3)3 -、N(SO2CF3)2 -、SCN-、CF3CF2SO3 -、C6F5SO3 -、CF3CO2 -、SO3F-、B(C6H5)4 -、CF3SO3 -、或上述的组合;(c)1至10重量份的纳米氧化物;以及(d)1至20重量份的黏着剂。
本公开一实施例提供的电池,包括:正极;负极;以及上述的电解质,夹设于该正极与该负极之间。
附图说明
图1为本公开一实施例中,复合电解质膜其logσ对1000/K的折线图。
图2与图3为本公开实施例中,不同电池的放电曲线。
图4与图5为本公开实施例中,不同电池的充放电曲线。
图6为本发明一实施例中,表面修饰有聚合物的Li7La3Zr2O12的IR图谱。
图7为本公开一实施例中,复合电解质膜其logσ对1000/K的折线图。
图8A、图9A、与图10A为本公开一实施例中,电池经电镀/剥离试验的电压-电容曲线。
图8B、图9B、与图10B为本公开一实施例中,电池的库仑效率对应电镀/剥离循环次数。
图11为本公开一实施例中,复合电解质膜其logσ对1000/K的折线图。
具体实施方式
本发明一实施例提供的电解质,包括:(a)100重量份的氧化系固态无机电解质;(b)20至70重量份的[Li(-OR1)n-OR2]Y,其中R1为C1-4的烷撑基,R2为C1-4的烷基,n介于2至100之间,且Y为PF6 -、BF4 -、AsF6 -、SbF6 -、ClO4 -、AlCl4 -、GaCl4 -、NO3 -、C(SO2CF3)3 -、N(SO2CF3)2 -、SCN-、CF3CF2SO3 -、C6F5SO3 -、CF3CO2 -、SO3F-、B(C6H5)4 -、CF3SO3 -、或上述的组合;(c)1至10重量份的纳米氧化物;以及(d)1至20重量份的黏着剂。上述电解质可为凝固态薄膜状或固态薄膜状。在一实施例中,氧化系固态无机电解质包括锂镧锆氧化物、锂镧钛氧化物、锂铝钛磷酸盐、其他类似物、或上述的组合。
若[Li(-OR1)n-OR2]Y的比例过低,则电解质膜的离子导电度偏低。若[Li(-OR1)n-OR2]Y的比例过高,则电解质膜的机械强度差。若n值过低,则电解质膜的机械强度不佳。若n值过高,则电解质膜的室温离子导电度不佳。在一实施例中,[Li(-OR1)n-OR2]Y的R1为乙撑基,R2为甲基,n为4,且Y为N(SO2CF3)2 -。
若纳米氧化物的比例过低,则成膜性不佳。若纳米氧化物的比例过高,则离子导电度不佳。在一实施例中,纳米氧化物包括氧化硅、氧化铝、氧化铈、氧化钛、或上述的组合。在一实施例中,纳米氧化物的尺寸介于5nm至100nm之间。若纳米氧化物的尺寸过小,则不易分散。若纳米氧化物的尺寸过大,则离子导电度不佳。
若黏着剂的比例过低,则无法成膜。若黏着剂的比例过高,则膜的性质硬脆。在一实施例中,黏着剂包括聚偏二氟乙烯、聚四氟乙烯、聚乙烯醇、聚乙二醇、羧甲基纤维素、丁苯橡胶、聚丙烯酸酯、聚丙烯腈、或上述的组合。
在本发明一实施例中,可先取R2(-OR1)n-OR2与LiY混合后形成[Li(-OR1)n-OR2]Y,再加入纳米氧化物以形成凝固态电解质。接着将氧化系固态无机电解质加入凝固态电解质后混合,再加入黏着剂即可形成有机-无机复合的电解质,并压制成膜,得到复合电解质膜。
在另一实施例中,上述电解质可进一步包含(e)1至20重量份的高分歧聚合物,且高分歧聚合物修饰氧化系固态无机电解质的表面。上述高分岐聚合物可改善有机无机兼容性,并提高复合电解质膜的离子传导度。若高分歧聚合物的比例过高,则离子导电度不佳。在一实施例中,上述高分歧聚合物与上述氧化系固态无机电解质表面之间具有键结。上述高分歧聚合物是由预聚物与碱促进剂交联反应而成,而预聚物是由具马来酰亚胺官能基的前驱物与路易斯碱的前驱物反应而成。举例来说,具马来酰亚胺官能基的前驱物的结构可为:
或上述的组合,其中R3为-CH2NHCH2-、-C2H4NHC2H4-、-C(O)CH2-、-CH2OCH2-、-C(O)-、-O-、-S-、-S-S-、-S(O)-、-CH2S(O)CH2-、-(O)S(O)-、-CH2(C6H4)CH2-、-CH2(C6H4)O-、-(CH2CH(CH3)O)-、苯撑基、联苯撑基、C2-8的烷撑基、 每一R6各自为-(CH2CH2)O-、苯撑基、或C2-8烷撑基。R4是C2-8的烷撑基、-C(O)-、-C(CH3)2-、-O-、-S-、-S-S-、-S(O)-、-(O)S(O)-、或-O(C6H4)C(CF3)2(C6H4)O-。
,每一R6各自为-(CH2CH2)O-、苯撑基、或C2-8烷撑基,a+b+c=5或6,且a,b,c大于或等于1。当m=4时,R5为 每一R6各自为-(CH2CH2)O-、苯撑基、或C2-8烷撑基。当m=8时,R5为其中m’=2-5。
,其中a’+b’=45、或
在一实施例中,电池,包括正极;负极;以及上述电解质,夹设于正极与负极之间。在一实施例中,正极材料可包含元素硫、有机硫化物、硫碳复合物、铝、钒、钛、铬、铜、钼、铌、铁、镍、钴及锰的锂化氧化物、锂化硫化物、锂化硒化物、锂化碲化物、锂化磷化物、锂化硅化物、锂化铝化物、锂化硼化物、或上述的组合。在一实施例中,负极材料可包含金属锂、锂合金、稳相球状碳(MCMB)、气相成长碳纤维(VGCF)、纳米碳管(CNT)、石墨烯、焦炭、石墨、碳黑、乙炔黑、碳纤维、玻璃质碳、锂钛氧化物、硅、硅基合金、锡、锡基合金、或上述的组合。
在一实施例中,正极的表面上覆盖有胶态电解质,且胶态电解质包括高分岐聚合物、锂盐、以及溶剂。上述胶态电解质位于电解质与正极之间,可解决正极采用高能量正极时的微短路问题。正极与胶态电解质的重量比可为100:0.01至100:1。上述锂盐可为LiPF6、LiBF4、LiAsF6、LiSbF6、LiClO4、LiAlCl4、LiGaCl4、LiNO3、LiC(SO2CF3)3、LiN(SO2CF3)2、LiSCN、LiO3SCF2CF3、LiC6F5SO3、LiO2CCF3、LiSO3F、LiB(C6H5)4、LiCF3SO3、或上述的组合。上述溶剂可为γ-丁基内酯(γ-butyrolactone,GBL)、碳酸乙烯酯(ethylene carbonate,EC)、碳酸丙烯酯(propylene carbonate,PC)、碳酸二乙酯(diethyl carbonate,DEC)、乙酸丙酯(propyl acetate,PA)、碳酸二甲酯(dimethyl carbonate,DMC)、碳酸甲乙酯(ethylmethylcarbonate,EMC)、或上述的组合。在一实施例中,负极的表面上覆盖有胶态电解质,且胶态电解质包括高分岐聚合物、锂盐、以及溶剂。上述胶态电解质位于电解质与负极之间,可解决内部微短路问题。负极与胶态电解质的重量比可为100:0.01至100:1。在另一实施例中,正极与负极的表面上均分别覆盖有胶态电解质。正极与胶态电解质的重量比可为100:0.01至100:1,负极与胶态电解质的重量比可为100:0.01至100:1。上述胶态电解质中的高分歧聚合物与前述的有机-无机复合电解质中的高分岐聚合物类似,亦由预聚物与碱促进剂交联反应而成,而预聚物是由具马来酰亚胺官能基的前驱物与路易斯碱的前驱物反应而成。至于具马来酰亚胺官能基的前驱物、路易斯碱、与碱促进剂的种类则与前述类似,在此不赘述。
在另一实施例中,提供一种电池,包括正极;负极;上述电解质,贴附于负极上;以及电解液,设置于电解质与负极之间。在一实施例中,可进一步包含隔离膜,设置于电解质与负极之间。电解液可为非水系电解液,且非水系电解液可为非水性金属盐电解液。非水性金属盐电解液可包含金属盐类与溶剂,其中金属盐类可包含LiPF6、LiBF4、LiAsF6、LiSbF6、LiClO4、LiAlCl4、LiGaCl4、LiNO3、LiC(SO2CF3)3、LiN(SO2CF3)2、LiSCN、LiO3SCF2CF3、LiC6F5SO3、LiO2CCF3、LiSO3F、LiB(C6H5)4及LiCF3SO3、或上述的组合。溶剂可包含碳酸乙烯酯、碳酸丙烯酯、碳酸丁烯酯、碳酸二丙基酯、酸酐、N-甲基吡咯烷酮、N-甲基甲酰胺、二甲基甲酰胺、γ-丁基内酯、乙腈、二甲亚砜、亚硫酸二甲酯、1,2-二甲氧基乙烷、1,2-二丁氧基乙烷、四氢呋喃、2-甲基四氢呋喃、环氧丙烷、乙酸甲酯、丁酸甲酯、丁酸乙酯、丙酸甲酯、丙酸乙酯、碳酸二甲酯、碳酸二乙酯、碳酸甲基乙基酯、或上述的组合。隔离膜可为聚乙烯、聚丙烯、陶瓷材料、或上述的组合。
现有的固态电池使用的无机系及有机系固态电解质,具有界面阻抗大、制程难度高、低离子传导率及机械强度不足的问题。上述实施例透过有机无机复合的方式,形成的之复合电解质具有电化学稳定性与机械/黏着强度。上述有机-无机复合方式可提升电极与电解质界面的兼容性。此外,以高分歧聚合物修饰氧化系固态无机电解质的表面,有助于加速锂离子的传导效率。
为了让本公开的上述和其他目的、特征、和优点能更明显易懂,下文特举数实施例配合所附图示,作详细说明如下:
【实施例1】
取0.222g的四乙二醇二甲醚(tetra(ethylene glycol)dimethyl ether,TEGDME)、0.287g的双三氟甲基磺酰亚胺锂盐(lithium bis(trifluoromethylsulphonyl)imide,LiTFSI)、与0.056g的SiO2(购自Degussa的Aerosil 812)混合后,形成凝固态电解质。
取50重量份的Li7La3Zr2O12(购自MTI Corporation的LLZO)与50重量份的凝固态电解质混合后,再加入7重量份的聚四氟乙烯高分子颗粒(购自群扬科技的聚四氟乙烯微粉末),碾压后无法形成复合电解质膜。另外取60重量份的Li7La3Zr2O12与40重量份的凝固态电解质混合后,再加入7重量份的四氟乙烯高分子颗粒,碾压后形成厚度为200微米的复合电解质膜(LLZOGS(64))。另外取70重量份的Li7La3Zr2O12与30重量份的凝固态电解质混合后,再加入7重量份的四氟乙烯高分子颗粒,碾压后形成厚度为200微米的复合电解质膜(LLZOGS(73))。另外取80重量份的Li7La3Zr2O12与20重量份的凝固态电解质与混合后,再加入7重量份的四氟乙烯高分子颗粒,碾压后形成厚度为200微米的复合电解质膜(LLZOGS(82))。另外取100重量份的Li7La3Zr2O12与7重量份的四氟乙烯高分子颗粒混合后,碾压后形成厚度为300微米的复合电解质膜,无法压到更薄且其室温离子导电度仅有0.00015mS/cm。离子导电度(σ)是以交流阻抗分析求得,在通以交流电的情况下,由7MHz扫描至100MHz,得到奈奎斯特(Nyquist)频率图,取虚阻抗(Z”)为零时的实阻抗(Z’)截距,并以下列公式计算:
σ=L/(AR)
L=两电极间的距离,R=电解质阻抗,A=电极面积。
量测上述复合电解质膜于不同温度(K)的离子导电度(σ,mS/cm),其logσ对1000/K的折线图如图1所示。
【实施例2】
取25重量份的聚乙二醇(购自Sigma-Aldrich)、70量份的锂铁磷酸盐、与5重量份的导电碳(购自TIMCAL的super P)混合后,涂布于铝箔上并干燥以作为正极。取LiTFSI(购自3M)与聚乙二醇的水溶液涂布于载体上,烘干后离型载体以作为高分子电解质膜。上述水溶液中的LiTFSI与聚乙二醇的锂氧原子比(Li/O)约为10。将高分子电解质膜夹设于上述正极与锂箔(负极)之间,即组成电池。接着于55℃下对电池进行循环充放电测试50次(0.3C充电/0.3C放电),其放电曲线如图2所示。在此实施例中,电解质主要含有LiTFSI,而电池的电容量在重复充放电后快速衰退,且放电平台下降。
另外取实施例1的复合电解质膜(含有40重量份的凝固态电解质与60重量份的Li7La3Zr2O12),夹设于上述正极与锂箔(负极)之间,即组成电池。接着于55℃下对电池进行循环充放电测试50次(0.3C充电/0.3C放电),其放电曲线如图3所示。在此实施例中,电解质含有LiTFSI、TEGDME、SiO2、与Li7La3Zr2O12,且电池的电容量在重复充放电50次后未明显衰退,且放电平台相对稳定。
【实施例3】
取3重量份的聚偏二氟乙烯(polyvinylidene difluoride,PVDF,购自Solvay)、95重量份的高电压氧化锂钴(购自北大先行的983HA)、与2重量份的导电碳(购自TIMCAL的Super P)混合后,涂布于铝箔上并干燥以作为高能量正极。取实施例1的复合电解质膜(含有40重量份的凝固态电解质与60重量份的Li7La3Zr2O12),夹设于上述高能量正极与锂箔(负极)之间,即组成电池。接着于55℃下对电池进行循环充放电测试(0.1C充电/0.1C放电),其充放电曲线如图4所示。由图4的充电曲线可知,此电池有内部微短路现象。
取1.19g的马来酰亚胺前驱物(购自大合化成工业的BMI1100)与1.953g的路易斯碱(购自Huntsman的Jeffamine ED900)均匀混合于液态有机电解液(含有1.1M的LiPF6的碳酸乙烯酯/碳酸丙烯酯/碳酸二乙酯(3/2/5,v/v/v)溶液)后,于室温下反应隔夜形成预聚物。接着将0.098g的碱促进剂(2,4-二甲基-2-咪唑啉)加入预聚物以进行原位聚合,形成固含量8wt%的胶态电解质。
接着将上述高能量正极含浸至胶态电解质中,使胶态电解质渗入高能量正极的表面孔洞。之后取出表面覆盖有胶态电质的高能量正极,秤重可知胶态电解质的重量。将实施例1的复合电解质膜(含有40重量份的凝固态电解质与60重量份的Li7La3Zr2O12)夹设于上述高能量正极与锂箔(负极)之间,即组成电池。上述复合电解质膜中的Li7La3Zr2O12与胶态电解质的重量比为100:1。上述胶态电解质位于高能量正极与复合电解质膜之间。接着于35℃下对电池进行循环充放电测试(0.1C充电/0.1C放电),其充放电曲线如图5所示。由图5的充电曲线可知,表面覆盖有胶态电解质的正极可改善内部微短路现象。
【实施例4】
取1.19g的马来酰亚胺前驱物(购自大合化成的BMI1100)与1.953g的路易斯碱(购自Huntsman的Jeffamine ED900)均匀混合于二甲基乙酰胺中反应形成预聚物,再将0.098g的碱促进剂(2,4-二甲基-2-咪唑啉)加入二甲基乙酰胺中形成高分歧聚合物溶液。将60重量份的Li7La3Zr2O12加入高分歧聚合物溶液中混合后,离心清洗干燥以得表面修饰有高分歧聚合物的Li7La3Zr2O12。经热重分析可知处理过后的样品含有1.6wt%的高分歧聚合物。取表面修饰有高分歧聚合物的Li7La3Zr2O12与40重量份实施例1的凝固态电解质混合后,再加入7重量份的四氟乙烯高分子颗粒,碾压后形成厚度为200微米的复合电解质膜。经IR分析Li7La3Zr2O12与表面修饰有高分歧聚合物的Li7La3Zr2O12,如图6所示。由图6可知,表面修饰有高分歧聚合物的Li7La3Zr2O12在约1600cm-1至1770cm-1的间具有吸收(C=O键讯号),证明高分歧聚合物(含有C=O键)修饰Li7La3Zr2O12的表面。至于Li7La3Zr2O12,在1600cm-1至1770cm-1的间不具有吸收。
重复上述实验,差别在调整聚合物溶液的用量。最后形成的含有表面修饰高分歧聚合物的Li7La3Zr2O12的复合电解质膜中,经热重分析可知处理过后的样品含有6.6wt%的高分歧聚合物。此外重复上述实验,差别在调整高分歧聚合物溶液的用量。最后形成的含有表面修饰高分歧聚合物的Li7La3Zr2O12的复合电解质膜中,含有20wt%的高分歧聚合物。量测上述复合电解质膜于不同温度(K)的离子导电度(σ,mS/cm),其logσ对1000/K的折线图如图7所示。由图7可知,含有表面修饰有适当量的高分歧聚合物的Li7La3Zr2O12的复合电解质膜比含有Li7La3Zr2O12的复合电解质膜具有更高的离子导电度,但含有表面修饰过量高分歧聚合物的Li7La3Zr2O12的复合电解质膜其离子导电度反而比含有Li7La3Zr2O12的复合电解质膜低。
【实施例5】
取2.22g的四乙二醇二甲醚(tetra(ethylene glycol)dimethyl ether,TEGDME)与2.87g的双三氟甲基磺酰亚胺锂盐(lithium bis(trifluoromethylsulphonyl)imide,LiTFSI)混合后,形成液态电解质。将隔离膜(购自Celgard的2320)置于铜箔(正极)与锂箔(负极)之间以定义容置空间,再将液态电解质填入容置空间以形成电池。经电镀/剥离试验(量测条件:截止电压0.5V、电流7.12mA、电容量0.89mAh、温度55℃)后,发现锂箔表面生成锂枝结晶且生成死锂,造成电池的库仑效率低落。上述电镀/剥离试验的电压-电容曲线图8A所示,而库仑效率对应电镀/剥离循环次数如图8B所示。
另外取1.1M的LiPF6的碳酸乙烯酯/碳酸丙烯酯/碳酸二乙酯(3/2/5,v/v/v)溶液作为液态电解质。将隔离膜(购自Celgard的2320)置于铜箔(正极)与锂箔(负极)之间以定义容置空间,再将含LiPF6的液态电解质填入容置空间以形成电池。经电镀/剥离试验(量测条件:截止电压0.5V、电流7.12mA、电容量0.89mAh、温度55℃)后,发现锂箔表面生成锂枝结晶且生成死锂,造成电池的库仑效率低落。上述电镀/剥离试验的电压-电容曲线图9A所示,而库仑效率对应电镀/剥离循环次数如图9B所示。
另外取实施例1的复合电解质膜(含有40重量份的凝固态电解质与60重量份的Li7La3Zr2O12)夹设于铜箔(正极)与锂箔(负极)之间以形成电池。经电镀/剥离试验(量测条件:截止电压0.5V、电流7.12mA、电容量0.89mAh、温度55℃)后,即使电镀/剥离循环超过1000次仍有稳定的电压-电容曲线(与第一次电镀/剥离循环的电压-电容曲线几乎重迭),且库仑效率接近100%。上述电镀/剥离试验的电压-电容曲线图10A所示,而库仑效率对应电镀/剥离循环次数如图10B所示。
【实施例6】
将60重量份的Li7La3Zr2O12与聚偏二氟乙烯-聚六氟丙烯共聚物(polyvinylidenedifluoride-co-hexafluoro propylene,PVDF-HFP,购自Aldrich)混合后,离心清洗干燥以得表面修饰有聚合物(PVDF-HFP)的Li7La3Zr2O12。经热重分析可知,经表面修饰的LLZO中含有约7wt%的聚合物。取表面修饰有聚合物的Li7La3Zr2O12与40重量份实施例1的凝固态电解质混合后,再加入7重量份的四氟乙烯高分子颗粒,碾压后形成厚度为200微米的复合电解质膜。
量测此复合电解质膜于不同温度(K)的离子导电度(σ,mS/cm),其logσ对1000/K的折线图如图11所示。由图11可知,表面修饰有PVDF-HFP的Li7La3Zr2O12的复合电解质膜其离子导电度,反而比含有Li7La3Zr2O12的复合电解质膜低。
虽然本公开已以数个实施例公开如上,然其并非用以限定本公开,任何本技术领域普通技术人员,在不脱离本公开的精神和范围内,当可作任意的更动与润饰,因此本公开的保护范围当以权利要求书为准。
Claims (6)
1.一种电解质,包括:
陶瓷固态电解质;
四乙二醇二甲醚(TEGDME)与锂盐的混合物,且锂盐为LiBF4、LiAsF6、LiSbF6、LiClO4、LiAlCl4、LiGaCl4、LiNO3、LiC(SO2CF3)3、LiN(SO2CF3)2、LiCF3CF2SO3、LiC6F5SO3、LiCF3CO2、LiSO3F、LiB(C6H5)、LiCF3SO3、或上述的组合;
纳米氧化物;
黏着剂;以及
高分歧聚合物,该高分歧聚合物附着于该陶瓷固态电解质的表面。
2.根据权利要求1所述的电解质,其中该陶瓷固态电解质包括锂镧锆氧化物、锂镧钛氧化物、锂铝钛磷酸盐、或上述的组合。
3.根据权利要求1所述的电解质,其中该纳米氧化物包括氧化硅、氧化铝、氧化铈、氧化钛、或上述的组合。
4.根据权利要求1所述的电解质,其中该黏着剂包括聚偏二氟乙烯、聚四氟乙烯、聚乙烯醇、羧甲基纤维素、丁苯橡胶、聚丙烯酸酯、聚丙烯腈、或上述的组合。
5.根据权利要求1所述的电解质,其中该高分歧聚合物是由一预聚物与一碱促进剂交联反应而成,而该预聚物是由一具马来酰亚胺官能基的前驱物与一路易斯碱的前驱物反应而成。
6.一种电池,包括:
一正极;
一负极;以及
权利要求1所述的电解质,夹设于该正极与该负极之间。
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