CN113380972A - 一种低阻锂离子电池负极薄膜及其制备方法 - Google Patents
一种低阻锂离子电池负极薄膜及其制备方法 Download PDFInfo
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 56
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000004332 silver Substances 0.000 claims abstract description 29
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910052709 silver Inorganic materials 0.000 claims abstract description 26
- 239000000758 substrate Substances 0.000 claims abstract description 26
- 229910002986 Li4Ti5O12 Inorganic materials 0.000 claims abstract description 25
- 229910001961 silver nitrate Inorganic materials 0.000 claims abstract description 21
- 239000002243 precursor Substances 0.000 claims abstract description 18
- 229910009866 Ti5O12 Inorganic materials 0.000 claims abstract description 16
- 239000010936 titanium Substances 0.000 claims abstract description 11
- 239000011159 matrix material Substances 0.000 claims abstract description 9
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 9
- -1 titanium organic compound Chemical class 0.000 claims abstract description 9
- 238000000151 deposition Methods 0.000 claims abstract description 8
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 7
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 7
- 239000002904 solvent Substances 0.000 claims abstract description 7
- 239000011248 coating agent Substances 0.000 claims abstract description 6
- 238000000576 coating method Methods 0.000 claims abstract description 6
- 238000004528 spin coating Methods 0.000 claims abstract description 6
- 238000005118 spray pyrolysis Methods 0.000 claims abstract description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical group [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 9
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 8
- 229910052710 silicon Inorganic materials 0.000 claims description 8
- 239000010703 silicon Substances 0.000 claims description 8
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-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
- 238000000034 method Methods 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 5
- 238000005245 sintering Methods 0.000 claims description 4
- 239000007784 solid electrolyte Substances 0.000 claims description 4
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims description 3
- 229910009178 Li1.3Al0.3Ti1.7(PO4)3 Inorganic materials 0.000 claims description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 3
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 3
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims description 3
- 239000011574 phosphorus Substances 0.000 claims description 3
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 3
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 claims description 3
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 claims description 3
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 claims description 3
- RXPQRKFMDQNODS-UHFFFAOYSA-N tripropyl phosphate Chemical compound CCCOP(=O)(OCCC)OCCC RXPQRKFMDQNODS-UHFFFAOYSA-N 0.000 claims description 3
- 239000010408 film Substances 0.000 description 56
- 239000010409 thin film Substances 0.000 description 10
- 239000000463 material Substances 0.000 description 7
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 6
- 238000009830 intercalation Methods 0.000 description 5
- 230000002687 intercalation Effects 0.000 description 5
- 239000010410 layer Substances 0.000 description 5
- 238000009831 deintercalation Methods 0.000 description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- 239000010406 cathode material Substances 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 239000007773 negative electrode material Substances 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 229910032387 LiCoO2 Inorganic materials 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 239000011532 electronic conductor Substances 0.000 description 2
- 238000009713 electroplating Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- MGWGWNFMUOTEHG-UHFFFAOYSA-N 4-(3,5-dimethylphenyl)-1,3-thiazol-2-amine Chemical compound CC1=CC(C)=CC(C=2N=C(N)SC=2)=C1 MGWGWNFMUOTEHG-UHFFFAOYSA-N 0.000 description 1
- 229910011965 Li4Ti5O12In Inorganic materials 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
- H01M4/0402—Methods of deposition of the material
- H01M4/0404—Methods of deposition of the material by coating on electrode collectors
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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
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
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Abstract
本发明提供一种低阻锂离子电池负极薄膜的制备方法,包括如下步骤:将锂盐、硝酸银、钛有机化合物溶于溶剂中得到Li4Ti5O12/Ag前驱体溶液,其中,所述Li4Ti5O12/Ag前驱体溶液中锂元素与钛元素物质的量之比为(4‑4.2):5,通过喷雾热解或旋转镀膜法将所述Li4Ti5O12/Ag前驱体溶液沉积在基片上,将所述基片置于650‑750℃温度下热处理5‑30分钟,得到薄膜基体,所述薄膜基体中银元素的含量为0.5%‑5%;将所述薄膜基体置于0.01‑0.015mol/L硝酸银溶液中电镀沉积3‑8μm银镀层,得到低阻锂离子电池负极薄膜。本发明还提供一种低阻锂离子电池负极薄膜。本发明提供的低阻锂离子电池负极薄膜电阻率小。
Description
【技术领域】
本发明涉及锂离子电池技术领域,尤其涉及一种低阻锂离子电池负极薄膜及其制备方法。
【背景技术】
薄膜锂离子电池由于在智能卡、CMOS基集成电路、微设备等方面具有广泛的应用前景,受到各国学者的广泛关注,成为锂离子电池的研究热点。目前,阻碍薄膜锂离子电池应用的关键问题是薄膜电池内阻大,而薄膜电池内阻大的一个关键原因,是正负极薄膜的电阻率高。
Li4Ti5O12在充放电过程中,锂离子的嵌入和脱出对材料结构几乎没有影响,被称为零应变材料,是一种理想的嵌入型电极。Li4Ti5O12作为锂离子电池负极材料,嵌脱锂电位为1.55V,能与LiMn2O4、LiCoO2等4V级正极材料组成工作电压为2.4V的锂离子电池,是一种性能优良的锂离子电池负极材料。
但Li4Ti5O12的电子电导率低,Li4Ti5O12作为常规锂离子电池负极材料使用时,需要在Li4Ti5O12中加入了炭黑以提高材料的电子电导率。但制作薄膜电池时,由于薄膜是一次性制备,无法采用向负极薄膜中加入炭黑导电剂的常规锂离子电池制作工艺,导致电极薄膜的电阻较大。因此,实有必要提供一种低阻锂离子电池负极薄膜及其制备方法以解决上述问题。
【发明内容】
本发明公开了一种低阻锂离子电池负极薄膜及其制备方法,制得的低阻锂离子电池负极薄膜电阻较小。
为实现上述目的,本发明的技术方案为:
一种低阻锂离子电池负极薄膜的制备方法,包括如下步骤:
将锂盐、硝酸银、钛有机化合物溶于溶剂中得到Li4Ti5O12/Ag前驱体溶液,其中,所述Li4Ti5O12/Ag前驱体溶液中锂元素与钛元素物质的量之比为(4-4.2):5;
通过喷雾热解或旋转镀膜法将所述Li4Ti5O12/Ag前驱体溶液沉积在基片上,将所述基片置于650-750℃温度下热处理5-30分钟,得到薄膜基体,所述薄膜基体中银元素的含量为0.5%-5%;
将所述薄膜基体置于0.01-0.015mol/L硝酸银溶液中电镀沉积3-8μm银镀层,得到低阻锂离子电池负极薄膜。
优选的,所述溶剂为乙醇或乙二醇甲醚。
优选的,所述锂盐为醋酸锂或硝酸锂。
优选的,所述钛有机化合物为钛酸酯。
优选的,所述钛有机化合物为钛酸四丁酯或钛酸异丙酯。
优选的,所述含磷化合物为磷酸二氢铵、磷酸三甲酯、磷酸三乙酯、磷酸三丙酯或磷酸三丁酯。
优选的,所述基片为硅片、镀铂硅片或锂离子固体电解质Li1.3Al0.3Ti1.7(PO4)3烧结片。
本发明还提供一种低阻锂离子电池负极薄膜,采用上述的制备方法制备而成。
与相关技术相比,本发明提供的低阻锂离子电池负极薄膜的制备方法中,在Li4Ti5O12薄膜中分散少量银,银是优良的电子导体,且制备容易,能显著提升Li4Ti5O12薄膜的电子电导率,提升Li4Ti5O12薄膜的电化学性能。
【具体实施方式】
为了使本技术领域的人员更好地理解本发明实施例中的技术方案,并使本发明的上述目的、特征和优点能够更加明显易懂,下面对本发明的具体实施方式作进一步的说明。
一种低阻锂离子电池负极薄膜的制备方法,包括如下步骤:
将锂盐、硝酸银、钛有机化合物溶于溶剂中得到Li4Ti5O12/Ag前驱体溶液,其中,所述Li4Ti5O12/Ag前驱体溶液中锂元素与钛元素物质的量之比为(4-4.2):5;
通过喷雾热解或旋转镀膜法将所述Li4Ti5O12/Ag前驱体溶液沉积在基片上,将所述基片置于650-750℃温度下热处理5-30分钟,得到薄膜基体,所述薄膜基体中银元素的含量为0.5%-5%;
将所述薄膜基体置于硝酸银溶液中电镀沉积3-8μm银镀层,得到低阻锂离子电池负极薄膜。
锂元素与钛元素可反应生成Li4Ti5O12,Li4Ti5O12作为锂离子电池负极材料,能与LiMn2O4、LiCoO2等4V级正极材料组成工作电压为2.4V的锂离子电池。Li4Ti5O12在充放电过程中锂离子的嵌入和脱出对材料结构几乎没有影响,被称为零应变材料,是固态薄膜锂离子电池理想的负极材料。在高温条件下,由于硝酸银不能进入Li4Ti5O12晶体,硝酸银高温加热时就分解成单质银附着在所述材料基体表面,银是良好的电子导体,使得制备的低阻锂离子电池负极薄膜可同时提高Li4Ti5O12薄膜的离子和电子电导率,降低Li4Ti5O12薄膜电阻。
在硝酸银分解产生银的过程中,由于二氧化氮及氧气的逸动,会产生作用力,带动银粒子发生一定的位置偏移,从而使银层的分布不均,并且由于气体的产生,也会造成银层与薄膜基体的结合力强度不同。因此将所述薄膜基体置于硝酸银溶液中进行电镀,一方面可以增加银层的厚度,另一方面可以解除电镀的方式增加银层与薄膜基体之间的结合力,同时可以改善银层分布不均的问题。
优选的,所述溶剂为乙醇或乙二醇甲醚;所述锂盐为醋酸锂或硝酸锂;所述钛有机化合物为钛酸酯,具体为钛酸四丁酯或钛酸异丙酯;所述含磷化合物为磷酸二氢铵、磷酸三甲酯、磷酸三乙酯、磷酸三丙酯或磷酸三丁酯;所述基片为硅片、镀铂硅片或锂离子固体电解质Li1.3Al0.3Ti1.7(PO4)3烧结片。
本发明还提供一种低阻锂离子电池负极薄膜,采用上述的制备方法制备而成。
实施例1
将0.84摩尔醋酸锂、1.48克硝酸银溶于600毫升乙醇中,全部溶解后,滴加4毫升浓硝酸和20毫升乙酰丙酮,在不断搅拌下加入1.0摩尔钛酸四丁酯,得到Li4Ti5O12/Ag前驱体溶液。采用喷雾热解法将Li4Ti5O12/Ag前驱体溶液热解沉淀在硅基片上,沉积厚度达4微米时,将沉积薄膜于700℃热处理10分钟,得到Li4Ti5O12/Ag薄膜基体,所述薄膜基体中银元素的含量为0.5%。将所述薄膜基体置于0.01mol/L硝酸银溶液中电镀沉积3μm银镀层,得到低阻锂离子电池负极薄膜,其电阻率为8000欧/cm,为没分散银的Li4Ti5O12薄膜的46.5%。
实施例2
将0.21摩尔醋酸锂、0.74克硝酸银溶于150毫升乙醇中,全部溶解后,滴加1毫升浓硝酸和5毫升乙酰丙酮,在不断搅拌下加入0.25摩尔钛酸四丁酯,得到Li4Ti5O12/Ag前驱体溶液。采用旋转镀膜法将Li4Ti5O12/Ag前驱体溶液沉积在5mm厚的Li1.3Al0.3Ti1.7(PO4)3固体电解质烧结片上。每沉积一次湿膜后,以5℃/分钟的升温速度升到350℃恒温10分钟,冷却后,重复镀膜。在薄膜厚度达2微米后,将薄膜于700℃热处理10分钟,得到Li4Ti5O12/Ag薄膜基体,所述薄膜基体中银元素的含量为2%。将所述薄膜基体置于0.012mol/L硝酸银溶液中电镀沉积5μm银镀层,得到低阻锂离子电池负极薄膜,其电阻率为2000欧/cm,为没分散银的Li4Ti5O12薄膜的12.4%。
实施例3
将0.21摩尔醋酸锂、1.48克硝酸银溶于150毫升乙醇中,全部溶解后,滴加1毫升浓硝酸和5毫升乙酰丙酮,在不断搅拌下加入0.25摩尔钛酸四丁酯,得到Li4Ti5O12/Ag前驱体溶液。采用旋转镀膜法将Li4Ti5O12/Ag前驱体溶液沉积在硅基片上。每沉积一次湿膜后,以5℃/分钟的升温速度升到350℃恒温10分钟,冷却后,重复镀膜。在薄膜厚度达2微米后,将薄膜于650℃热处理10分钟,得到Li4Ti5O12/Ag薄膜基体,所述薄膜基体中银元素的含量为5%。将所述薄膜基体置于0.015mol/L硝酸银溶液中电镀沉积8μm银镀层,得到低阻锂离子电池负极薄膜,其电阻率为800欧/cm,为没分散银的Li4Ti5O12薄膜的6.15%。
与相关技术相比,本发明提供的低阻锂离子电池负极薄膜的制备方法中,在Li4Ti5O12薄膜中分散少量银,银是优良的电子导体,且制备容易,能显著提升Li4Ti5O12薄膜的电子电导率,提升Li4Ti5O12薄膜的电化学性能。
Claims (8)
1.一种低阻锂离子电池负极薄膜的制备方法,其特征在于,包括如下步骤:
将锂盐、硝酸银、钛有机化合物溶于溶剂中得到Li4Ti5O12/Ag前驱体溶液,其中,所述Li4Ti5O12/Ag前驱体溶液中锂元素与钛元素物质的量之比为(4-4.2):5;
通过喷雾热解或旋转镀膜法将所述Li4Ti5O12/Ag前驱体溶液沉积在基片上,将所述基片置于650-750℃温度下热处理5-30分钟,得到Li4Ti5O12/Ag薄膜基体,所述薄膜基体中银元素的含量为0.5%-5%;
将所述薄膜基体置于0.01-0.015mol/L硝酸银溶液中电镀沉积3-8μm银镀层,得到低阻锂离子电池负极薄膜。
2.根据权利要求1所述的低阻锂离子电池负极薄膜的制备方法,其特征在于,所述溶剂为乙醇或乙二醇甲醚。
3.根据权利要求1所述的低阻锂离子电池负极薄膜的制备方法,其特征在于,所述锂盐为醋酸锂或硝酸锂。
4.根据权利要求1所述的低阻锂离子电池负极薄膜的制备方法,其特征在于,所述钛有机化合物为钛酸酯。
5.根据权利要求4所述的低阻锂离子电池负极薄膜的制备方法,其特征在于,所述钛有机化合物为钛酸四丁酯或钛酸异丙酯。
6.根据权利要求1所述的低阻锂离子电池负极薄膜的制备方法,其特征在于,所述含磷化合物为磷酸二氢铵、磷酸三甲酯、磷酸三乙酯、磷酸三丙酯或磷酸三丁酯。
7.根据权利要求1所述的低阻锂离子电池负极薄膜的制备方法,其特征在于,所述基片为硅片、镀铂硅片或锂离子固体电解质Li1.3Al0.3Ti1.7(PO4)3烧结片。
8.一种低阻锂离子电池负极薄膜,其特征在于,采用权利要求1-7任一项所述的制备方法制备而成。
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