CN111740075A - Flexible electrodes and flexible batteries based on carbonized silk fabrics - Google Patents
Flexible electrodes and flexible batteries based on carbonized silk fabrics Download PDFInfo
- Publication number
- CN111740075A CN111740075A CN202010548569.7A CN202010548569A CN111740075A CN 111740075 A CN111740075 A CN 111740075A CN 202010548569 A CN202010548569 A CN 202010548569A CN 111740075 A CN111740075 A CN 111740075A
- Authority
- CN
- China
- Prior art keywords
- flexible
- electrode
- lithium
- sulfur
- silk fabric
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000004744 fabric Substances 0.000 title claims abstract description 173
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 124
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 79
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 60
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 52
- 239000011593 sulfur Substances 0.000 claims abstract description 52
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000007772 electrode material Substances 0.000 claims abstract description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 41
- 239000011230 binding agent Substances 0.000 claims description 41
- 239000002904 solvent Substances 0.000 claims description 27
- 239000007774 positive electrode material Substances 0.000 claims description 25
- 239000011267 electrode slurry Substances 0.000 claims description 24
- 238000010438 heat treatment Methods 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 22
- 239000002482 conductive additive Substances 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 239000003792 electrolyte Substances 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 14
- 239000003960 organic solvent Substances 0.000 claims description 14
- 238000003763 carbonization Methods 0.000 claims description 13
- 239000011261 inert gas Substances 0.000 claims description 13
- 239000000463 material Substances 0.000 claims description 13
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 claims description 12
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 claims description 12
- 239000007773 negative electrode material Substances 0.000 claims description 12
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 claims description 9
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 claims description 9
- 239000006230 acetylene black Substances 0.000 claims description 7
- 239000002041 carbon nanotube Substances 0.000 claims description 7
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 7
- 229910021389 graphene Inorganic materials 0.000 claims description 7
- 239000003273 ketjen black Substances 0.000 claims description 7
- 229910002804 graphite Inorganic materials 0.000 claims description 6
- 239000010439 graphite Substances 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 6
- 150000003464 sulfur compounds Chemical class 0.000 claims description 6
- 238000000576 coating method Methods 0.000 claims description 5
- 230000008021 deposition Effects 0.000 claims description 5
- 238000007363 ring formation reaction Methods 0.000 claims description 5
- 208000005156 Dehydration Diseases 0.000 claims description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000011248 coating agent Substances 0.000 claims description 4
- 230000018044 dehydration Effects 0.000 claims description 4
- 238000006297 dehydration reaction Methods 0.000 claims description 4
- 229910044991 metal oxide Inorganic materials 0.000 claims description 4
- 150000004706 metal oxides Chemical class 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 239000010703 silicon Substances 0.000 claims description 4
- 238000005520 cutting process Methods 0.000 claims description 3
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 claims description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims 2
- BLJNPOIVYYWHMA-UHFFFAOYSA-N alumane;cobalt Chemical compound [AlH3].[Co] BLJNPOIVYYWHMA-UHFFFAOYSA-N 0.000 claims 1
- 229910052759 nickel Inorganic materials 0.000 claims 1
- 238000002360 preparation method Methods 0.000 abstract description 25
- 239000005077 polysulfide Substances 0.000 abstract description 15
- 229920001021 polysulfide Polymers 0.000 abstract description 15
- 150000008117 polysulfides Polymers 0.000 abstract description 15
- 210000001787 dendrite Anatomy 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 7
- 230000009286 beneficial effect Effects 0.000 abstract description 5
- 229910052751 metal Inorganic materials 0.000 abstract description 5
- 239000002184 metal Substances 0.000 abstract description 5
- 230000008901 benefit Effects 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 abstract 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 16
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 15
- 229910052799 carbon Inorganic materials 0.000 description 13
- 239000002131 composite material Substances 0.000 description 13
- 238000010586 diagram Methods 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 8
- 229910052786 argon Inorganic materials 0.000 description 8
- -1 nickel-cobalt-aluminum Chemical compound 0.000 description 8
- 240000000249 Morus alba Species 0.000 description 7
- 235000008708 Morus alba Nutrition 0.000 description 7
- 238000000151 deposition Methods 0.000 description 7
- 238000001878 scanning electron micrograph Methods 0.000 description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 229910018091 Li 2 S Inorganic materials 0.000 description 5
- 229910013553 LiNO Inorganic materials 0.000 description 5
- 239000004743 Polypropylene Substances 0.000 description 5
- GJEAMHAFPYZYDE-UHFFFAOYSA-N [C].[S] Chemical compound [C].[S] GJEAMHAFPYZYDE-UHFFFAOYSA-N 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 239000000835 fiber Substances 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 description 5
- 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 description 5
- 230000004048 modification Effects 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 239000002985 plastic film Substances 0.000 description 5
- 229920006255 plastic film Polymers 0.000 description 5
- 229920001155 polypropylene Polymers 0.000 description 5
- 229920000049 Carbon (fiber) Polymers 0.000 description 4
- 108010022355 Fibroins Proteins 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 238000012512 characterization method Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- DOTMOQHOJINYBL-UHFFFAOYSA-N molecular nitrogen;molecular oxygen Chemical compound N#N.O=O DOTMOQHOJINYBL-UHFFFAOYSA-N 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 108010013296 Sericins Proteins 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 238000005452 bending Methods 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 239000011889 copper foil Substances 0.000 description 3
- 230000001351 cycling effect Effects 0.000 description 3
- 239000002003 electrode paste Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 241000255789 Bombyx mori Species 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 238000004070 electrodeposition Methods 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910001947 lithium oxide Inorganic materials 0.000 description 2
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 229910052754 neon Inorganic materials 0.000 description 2
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 2
- 230000006911 nucleation Effects 0.000 description 2
- 238000010899 nucleation Methods 0.000 description 2
- 108090000623 proteins and genes Proteins 0.000 description 2
- 102000004169 proteins and genes Human genes 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000013112 stability test Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- 241000255783 Bombycidae Species 0.000 description 1
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 240000003183 Manihot esculenta Species 0.000 description 1
- 235000016735 Manihot esculenta subsp esculenta Nutrition 0.000 description 1
- 235000004443 Ricinus communis Nutrition 0.000 description 1
- 208000013201 Stress fracture Diseases 0.000 description 1
- ZQRRBZZVXPVWRB-UHFFFAOYSA-N [S].[Se] Chemical compound [S].[Se] ZQRRBZZVXPVWRB-UHFFFAOYSA-N 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- XZWVIKHJBNXWAT-UHFFFAOYSA-N argon;azane Chemical compound N.[Ar] XZWVIKHJBNXWAT-UHFFFAOYSA-N 0.000 description 1
- 238000005899 aromatization reaction Methods 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000002837 carbocyclic group Chemical group 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001523 electrospinning Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 239000012943 hotmelt Substances 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- QEXMICRJPVUPSN-UHFFFAOYSA-N lithium manganese(2+) oxygen(2-) Chemical compound [O-2].[Mn+2].[Li+] QEXMICRJPVUPSN-UHFFFAOYSA-N 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920000131 polyvinylidene Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 108090000765 processed proteins & peptides Proteins 0.000 description 1
- 230000001603 reducing effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000003463 sulfur Chemical class 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 238000003828 vacuum filtration Methods 0.000 description 1
Images
Classifications
-
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
-
- 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
-
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
-
- 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
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/663—Selection of materials containing carbon or carbonaceous materials as conductive part, e.g. graphite, carbon fibres
-
- 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
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
本发明提供一种基于碳化蚕丝织物的柔性电极,包含碳化蚕丝织物和与该碳化蚕丝织物复合的电极活性材料。本发明的柔性电极尤其为柔性锂负极和柔性硫正极。本发明还提供一种包含该柔性电极的柔性电池,尤其是柔性锂硫电池。本发明的柔性电极和柔性电池具有以下优点:碳化蚕丝织物的原材料来源广,制备过程简单,绿色环保,成本低;碳化蚕丝织物具有三维空间结构,柔性和导电性良好,且存在丰富的氮氧掺杂结构,对多硫化物和金属锂均具更好的亲和性,可以抑制锂枝晶的生长,抑制多硫化物在锂硫电池中的“穿梭效应”,提高电池的循环稳定性;碳化蚕丝织物的面质量较轻,有利于提高电池的能量密度。
The present invention provides a flexible electrode based on carbonized silk fabric, comprising carbonized silk fabric and an electrode active material compounded with the carbonized silk fabric. The flexible electrodes of the present invention are especially flexible lithium negative electrodes and flexible sulfur positive electrodes. The present invention also provides a flexible battery comprising the flexible electrode, especially a flexible lithium-sulfur battery. The flexible electrode and flexible battery of the invention have the following advantages: the carbonized silk fabric has a wide source of raw materials, the preparation process is simple, green and environmentally friendly, and the cost is low; the carbonized silk fabric has a three-dimensional spatial structure, good flexibility and conductivity, and there are abundant nitrogen oxides The doping structure has better affinity for polysulfides and metal lithium, which can inhibit the growth of lithium dendrites, inhibit the "shuttle effect" of polysulfides in lithium-sulfur batteries, and improve the cycle stability of the battery; The surface quality of carbonized silk fabric is lighter, which is beneficial to improve the energy density of the battery.
Description
技术领域technical field
本发明属于电池技术领域,具体地涉及基于碳化蚕丝织物的柔性电极和柔性电池,更具体地涉及一种包含碳化蚕丝织物的柔性电极,尤其是柔性锂负极和柔性硫正极,以及一种包含该柔性电极的柔性电池,尤其是柔性锂硫电池。The invention belongs to the technical field of batteries, in particular to a flexible electrode and a flexible battery based on carbonized silk fabrics, and more particularly to a flexible electrode comprising carbonized silk fabrics, especially a flexible lithium negative electrode and a flexible sulfur positive electrode, and a flexible electrode comprising the carbonized silk fabric Flexible batteries with flexible electrodes, especially flexible lithium-sulfur batteries.
背景技术Background technique
近年来,随着卷轴式显示屏、电子纺织品、软体机器人、物联网系统和生物电子产品等柔性可穿戴电子产品的快速发展与新兴应用,急需开发一种轻薄、可柔软弯折、能量密度高且性能稳定的电池,为各种可穿戴与柔性电子器件提供电源。目前采用金属箔作为集流体的刚性锂离子电池在反复弯折时会出现疲劳断裂以及活性物质剥离,易造成电化学与机械性能衰减;同时锂离子电池采用的层状嵌锂活性材料理论比容量不高,需要使用较厚的电极,故难以实现锂电池优异的柔韧性与高能量密度。In recent years, with the rapid development and emerging applications of flexible wearable electronic products such as scroll-type displays, electronic textiles, soft robots, Internet of Things systems, and bioelectronic products, there is an urgent need to develop a thin, flexible, flexible, high-energy density The battery with stable performance provides power for various wearable and flexible electronic devices. At present, rigid lithium-ion batteries that use metal foils as current collectors will suffer fatigue fracture and active material peeling when they are repeatedly bent, which is easy to cause electrochemical and mechanical performance degradation. It is not high and needs to use thicker electrodes, so it is difficult to achieve the excellent flexibility and high energy density of lithium batteries.
锂硫电池作为下一代的锂电池技术,使用硫及金属锂分别作为电池的正负极材料,具有极高比容量(锂:3860mAh/kg;硫:1675mAh/kg)的理论优势,非常适合可穿戴与柔性电子器件产品的应用,引起了国内外的广泛关注。但是,锂硫电池的应用仍面临众多挑战。在负极方面,锂金属充放电过程中巨大的体积变化和锂枝晶生长易导致负极表面SEI膜连续破坏以及电解液的不断消耗;在正极方面,电池使用过程中会发生正极硫溶出现象,产生多硫化物(如Li2S4、Li2S6、Li2S8等),这些多硫化物可以溶于电解液并穿过电池隔膜,导致活性硫在循环过程中不断损失以及电解液消耗。可见,以上因素均会导致锂硫电池的电化学性能不稳定。Lithium-sulfur battery, as the next generation of lithium battery technology, uses sulfur and metal lithium as the positive and negative electrode materials of the battery, and has the theoretical advantage of extremely high specific capacity (lithium: 3860mAh/kg; sulfur: 1675mAh/kg). The application of wearable and flexible electronic device products has attracted extensive attention at home and abroad. However, the application of lithium-sulfur batteries still faces many challenges. On the negative electrode side, the huge volume change and lithium dendrite growth during the charging and discharging process of lithium metal can easily lead to the continuous destruction of the SEI film on the negative electrode surface and the continuous consumption of electrolyte; Polysulfides (such as Li 2 S 4 , Li 2 S 6 , Li 2 S 8 , etc.), which can dissolve in the electrolyte and pass through the battery separator, resulting in continuous loss of active sulfur during cycling and electrolyte consumption . It can be seen that the above factors will lead to the unstable electrochemical performance of lithium-sulfur batteries.
采用高比面积柔性导电基材替换金属箔作为集流体,是提高锂硫电池电化学性能与机械柔韧性的一种重要途径。目前锂硫电极柔性集流体基材主要包括两类,一类是碳纳米管、石墨烯、纤维素碳纸,另一类是碳织物。碳纸具有质量轻和导电性较高等特点,可以将锂硫活性物质直接沉积在薄膜碳纸上制备柔性电极,进而可组装轻质柔性锂硫电池,但该类柔性锂硫电池一般能量密度较低、弯折稳定性较差。碳织物具有较高柔韧性、多孔网状结构以及良好的化学稳定性等优势,利用其制备的锂硫电极具有优异的机械柔韧性。国内外研究团队已尝试利用真空抽滤、液体浸渍、电沉积、热熔等方式在碳织物表面负载高活性锂硫物质来实现柔性锂硫电极的制备。但是,商用碳化织物面质量密度较大、对多硫化物和金属锂均具有较差的亲和性,无法有效抑制多硫化物的穿梭效应和锂枝晶生长,往往造成碳织物锂硫电池的电化学与机械稳定性较差。虽然大量前期工作通过表面改性(如异质原子掺杂、金属硫化物修饰、过渡金属涂层等)改善了碳化织物锂硫电池的电化学与机械稳定性,但多数表面改性过程繁琐复杂以及界面稳定性不佳。因此,利用简单有效的方法来实现高性能柔性锂硫电极与全电池仍具有较大的挑战性。Replacing metal foils with high-specific-area flexible conductive substrates as current collectors is an important way to improve the electrochemical performance and mechanical flexibility of lithium-sulfur batteries. At present, there are mainly two types of flexible current collector substrates for lithium-sulfur electrodes, one is carbon nanotubes, graphene, and cellulose carbon paper, and the other is carbon fabrics. Carbon paper has the characteristics of light weight and high conductivity. Lithium-sulfur active materials can be directly deposited on thin-film carbon paper to prepare flexible electrodes, and then light and flexible lithium-sulfur batteries can be assembled. However, such flexible lithium-sulfur batteries generally have higher energy density. Low, poor bending stability. Carbon fabrics have the advantages of high flexibility, porous network structure and good chemical stability, and the lithium-sulfur electrodes prepared by using them have excellent mechanical flexibility. Research teams at home and abroad have tried to use vacuum filtration, liquid impregnation, electrodeposition, hot melting, etc. to load highly active lithium-sulfur substances on the surface of carbon fabrics to realize the preparation of flexible lithium-sulfur electrodes. However, commercial carbonized fabrics have high surface mass density and poor affinity for polysulfides and metallic lithium, which cannot effectively inhibit the shuttle effect of polysulfides and the growth of lithium dendrites, which often results in the failure of carbon fabrics for lithium-sulfur batteries. Electrochemical and mechanical stability is poor. Although a large number of previous works have improved the electrochemical and mechanical stability of carbonized fabric lithium-sulfur batteries through surface modification (such as heteroatom doping, metal sulfide modification, transition metal coating, etc.), most surface modification processes are cumbersome and complicated. and poor interface stability. Therefore, it is still challenging to realize high-performance flexible lithium-sulfur electrodes and full batteries using simple and effective methods.
发明内容SUMMARY OF THE INVENTION
本发明的目的在于解决现有的碳化织物和碳化织物锂硫电池存在的上述技术问题,并通过基于碳化蚕丝织物的柔性电极和柔性电池的创新性技术方案实现了上述目的。The purpose of the present invention is to solve the above-mentioned technical problems existing in the existing carbonized fabric and carbonized fabric lithium-sulfur batteries, and achieve the above-mentioned purpose through the innovative technical scheme of the flexible electrode and flexible battery based on the carbonized silk fabric.
具体地,在第一方面,本发明提供一种柔性电极,该柔性电极包含碳化蚕丝织物和与该碳化蚕丝织物复合的电极活性材料。Specifically, in a first aspect, the present invention provides a flexible electrode comprising a carbonized silk fabric and an electrode active material compounded with the carbonized silk fabric.
进一步地,该碳化蚕丝织物通过以下方法制得:在惰性气体保护下,将蚕丝织物在第一温度下进行脱水处理,在第二温度下进行预环化处理,并在第三温度下进行炭化处理,得到该炭化蚕丝织物。Further, the carbonized silk fabric is prepared by the following method: under the protection of an inert gas, the silk fabric is dehydrated at a first temperature, pre-cyclized at a second temperature, and carbonized at a third temperature. treatment to obtain the carbonized silk fabric.
更进一步地,在惰性气体保护下,将蚕丝织物在100℃-200℃之间的第一温度下进行脱水处理1-2h,然后在300℃-400℃之间的第二温度下进行环化处理2-3h,然后在950℃-1100℃之间的第三温度下进行碳化处理1-2h,蚕丝织物升温到第一温度、第二温度和第三温度的升温速率独立地为2℃-10℃/min。Further, under the protection of inert gas, the silk fabric is dehydrated at a first temperature between 100°C and 200°C for 1-2 hours, and then cyclized at a second temperature between 300°C and 400°C. Treated for 2-3h, then carbonized at a third temperature between 950℃-1100℃ for 1-2h, the heating rate of the silk fabric to the first temperature, the second temperature and the third temperature was independently 2℃- 10°C/min.
在本发明的柔性电极的一个实施方案中,该电极活性材料为负极活性材料,该负极活性材料为锂金属、硅、石墨或金属氧化物。优选地,该负极活性材料为锂金属,该柔性电极为柔性锂负极。In one embodiment of the flexible electrode of the present invention, the electrode active material is a negative electrode active material, and the negative electrode active material is lithium metal, silicon, graphite or metal oxide. Preferably, the negative electrode active material is lithium metal, and the flexible electrode is a flexible lithium negative electrode.
进一步地,该柔性锂负极通过以下方法制备:将该碳化蚕丝织物裁剪为大小合适的碳化蚕丝织物极片,与锂金属电极相匹配,组装为半电池;在电流大小恒定的条件下,将锂金属定量沉积到碳化蚕丝织物极片上;然后取出沉积有锂金属的碳化蚕丝织物极片,用有机溶剂冲洗,干燥,得到该柔性锂负极。Further, the flexible lithium negative electrode is prepared by the following method: cutting the carbonized silk fabric into a carbonized silk fabric pole piece of suitable size, matching with the lithium metal electrode, and assembling it into a half-cell; under the condition of constant current, the lithium Metal is quantitatively deposited on the carbonized silk fabric pole piece; then the carbonized silk fabric pole piece deposited with lithium metal is taken out, rinsed with an organic solvent, and dried to obtain the flexible lithium negative electrode.
进一步地,电流大小在0.1-1mA cm-2的范围内,锂金属的沉积量在1-20mAh cm-2的范围内。Further, the current magnitude is in the range of 0.1-1 mA cm- 2 , and the deposition amount of lithium metal is in the range of 1-20 mAh cm- 2 .
在本发明的柔性电极的另一些实施方案中,该电极活性材料为正极活性材料,该正极活性材料包含硫元素,该柔性电极为柔性硫正极。In other embodiments of the flexible electrode of the present invention, the electrode active material is a positive electrode active material, the positive electrode active material comprises elemental sulfur, and the flexible electrode is a flexible sulfur positive electrode.
进一步地,该柔性电极通过以下方法制备:将硫粉与导电添加剂按照(2-3):1的质量比混合并充分研磨,将研磨好的混合物在惰性气体保护下在150-160℃下进行水热反应12-16h,得到硫复合物;将所得的硫复合物和粘结剂按照(8-9):1的质量比在适量的溶剂中充分混合,得到正极浆料;然后将所得的正极浆料涂覆于该碳化蚕丝织物上,在60℃-80℃下真空干燥12-16h以去除溶剂,得到该柔性电极,即柔性硫正极。Further, the flexible electrode is prepared by the following method: mixing sulfur powder and conductive additive according to the mass ratio of (2-3): 1 and fully grinding, and carrying out the grinding process at 150-160° C. under the protection of inert gas The hydrothermal reaction is carried out for 12-16h to obtain a sulfur compound; the obtained sulfur compound and the binder are fully mixed in an appropriate amount of solvent according to the mass ratio of (8-9):1 to obtain a positive electrode slurry; then the obtained The positive electrode slurry is coated on the carbonized silk fabric, and vacuum-dried at 60° C.-80° C. for 12-16 hours to remove the solvent to obtain the flexible electrode, that is, a flexible sulfur positive electrode.
进一步地,导电添加剂为乙炔黑、科琴黑、Super P、Super C45、碳纳米管、石墨烯中的一种或多种,粘结剂为水系粘结剂或者有机溶剂系粘结剂。Further, the conductive additive is one or more of acetylene black, Ketjen black, Super P, Super C45, carbon nanotubes, and graphene, and the binder is a water-based binder or an organic solvent-based binder.
在本发明的柔性电极的又一些实施方案中,该电极活性材料为正极活性材料,该正极活性材料为镍钴锰三元材料(NCM)、钴酸锂(LCO)、磷酸铁锂(LFP)、镍钴铝三元材料(NCA)、锰酸锂(LMO)、镍酸锂(LNO)中的一种或多种。In still other embodiments of the flexible electrode of the present invention, the electrode active material is a positive electrode active material, and the positive electrode active material is a nickel-cobalt-manganese ternary material (NCM), lithium cobalt oxide (LCO), lithium iron phosphate (LFP) , one or more of nickel-cobalt-aluminum ternary material (NCA), lithium manganate (LMO), and lithium nickelate (LNO).
进一步地,该柔性电极通过以下方法制备:将该正极活性材料与导电添加剂、粘结剂按照(4-9):(1-2):1的质量比在适量的溶剂中混合均匀,得到正极浆料;然后将所得的正极浆料均匀涂覆于该碳化蚕丝织物上,在60℃-80℃下真空干燥12-16h以去除溶剂,得到该柔性电极。Further, the flexible electrode is prepared by the following method: the positive electrode active material, the conductive additive and the binder are uniformly mixed in an appropriate amount of solvent according to the mass ratio of (4-9):(1-2):1 to obtain a positive electrode slurry; then uniformly coat the obtained positive electrode slurry on the carbonized silk fabric, and vacuum dry at 60°C-80°C for 12-16 hours to remove the solvent to obtain the flexible electrode.
进一步地,导电添加剂为乙炔黑、科琴黑、Super P、Super C45、碳纳米管、石墨烯中的一种或多种,粘结剂为水系粘结剂或者有机溶剂系粘结剂。Further, the conductive additive is one or more of acetylene black, Ketjen black, Super P, Super C45, carbon nanotubes, and graphene, and the binder is a water-based binder or an organic solvent-based binder.
在另一方面,本发明提供一种柔性电池,其包括电极、隔膜和电解液,该电极包括正极和负极,该隔膜位于正极和负极之间,该电极包括根据本发明第一方面的柔性电极。In another aspect, the present invention provides a flexible battery comprising an electrode, a separator and an electrolyte, the electrode comprising a positive electrode and a negative electrode, the separator being positioned between the positive electrode and the negative electrode, the electrode comprising the flexible electrode according to the first aspect of the present invention .
在本发明的柔性电池的一些实施方案中,该负极为根据本发明第一方面的柔性锂负极。In some embodiments of the flexible battery of the present invention, the negative electrode is a flexible lithium negative electrode according to the first aspect of the present invention.
在本发明的柔性电池的另一些实施方案中,该正极为根据本发明第一方面的柔性硫正极。In other embodiments of the flexible battery of the present invention, the positive electrode is a flexible sulfur positive electrode according to the first aspect of the present invention.
在本发明的柔性电池的又一些实施方案中,该负极为根据本发明第一方面的柔性锂负极,该正极为根据本发明第一方面的柔性硫正极,该柔性电池为柔性锂硫电池。In further embodiments of the flexible battery of the present invention, the negative electrode is a flexible lithium negative electrode according to the first aspect of the present invention, the positive electrode is a flexible sulfur positive electrode according to the first aspect of the present invention, and the flexible battery is a flexible lithium-sulfur battery.
本发明的有益效果:Beneficial effects of the present invention:
本发明以基于蚕丝织物碳化衍生的碳化蚕丝织物作为柔性碳基材料,首次将碳化蚕丝织物应用于制备柔性电极(包括柔性正极和柔性负极)和柔性电池,包括优选的柔性锂负极和柔性硫正极,以及优选的柔性锂硫电池,具有以下有益效果:In the present invention, carbonized silk fabrics derived from carbonization of silk fabrics are used as flexible carbon-based materials, and carbonized silk fabrics are applied to the preparation of flexible electrodes (including flexible positive electrodes and flexible negative electrodes) and flexible batteries for the first time, including preferred flexible lithium negative electrodes and flexible sulfur positive electrodes. , and the preferred flexible lithium-sulfur battery, with the following beneficial effects:
(1)碳化蚕丝织物的原材料来源广,制备过程简单,绿色环保,成本低。(1) The raw materials of carbonized silk fabrics are widely sourced, the preparation process is simple, green and environmentally friendly, and the cost is low.
(2)碳化蚕丝织物具有三维空间结构,柔性和导电性良好,且存在丰富的氮氧掺杂结构,与商业碳化织物相比,对多硫化物和金属锂均具更好的亲和性。因此,碳化蚕丝织物用于锂负极,可以降低局部电流密度,引导锂金属均匀成核,抑制锂枝晶的生长;用于硫正极,可以缓冲电池循环过程中硫体积变化引起的应力,吸附硫正极上产生的多硫化物,抑制锂硫电池的“穿梭效应”,从而提高电池的循环稳定性。(2) The carbonized silk fabric has a three-dimensional spatial structure, good flexibility and electrical conductivity, and has abundant nitrogen-oxygen doping structure. Compared with commercial carbonized fabrics, it has better affinity for polysulfides and metallic lithium. Therefore, when carbonized silk fabric is used for lithium anode, it can reduce the local current density, guide the uniform nucleation of lithium metal, and inhibit the growth of lithium dendrites; when used in sulfur cathode, it can buffer the stress caused by the change of sulfur volume during battery cycling and adsorb sulfur The polysulfides generated on the positive electrode inhibit the "shuttle effect" of lithium-sulfur batteries, thereby improving the battery's cycle stability.
(3)与常用的商业碳布相比,碳化蚕丝织物的面质量较轻(商业碳布的面质量通常为12.6mg cm-2,碳化蚕丝织物的面质量为1.8-6.3mg cm-2),有利于提高电池的能量密度。(3) Compared with the commonly used commercial carbon cloth, the surface quality of carbonized silk fabric is lighter (the surface quality of commercial carbon cloth is usually 12.6 mg cm -2 , and the surface quality of carbonized silk fabric is 1.8-6.3 mg cm -2 ) , which is beneficial to improve the energy density of the battery.
(4)本发明的柔性锂负极和柔性硫正极表现出良好的柔性和循环稳定性,可以相互匹配或与其他柔性电极匹配组装成柔性电池,以提高柔性电池的能量密度和循环性能,具有良好的应用前景。(4) The flexible lithium negative electrode and the flexible sulfur positive electrode of the present invention exhibit good flexibility and cycle stability, and can be matched with each other or matched with other flexible electrodes to form a flexible battery, so as to improve the energy density and cycle performance of the flexible battery, and have good flexibility. application prospects.
附图说明Description of drawings
图1显示本发明实施例1和2制得的碳化蚕丝布的SEM图,其中(a)和(b)显示实施例1制得的碳化蚕丝布的SEM图,(c)和(d)显示实施例2制得的碳化蚕丝布的SEM图;Figure 1 shows the SEM images of the carbonized silk cloth prepared in Examples 1 and 2 of the present invention, wherein (a) and (b) show the SEM images of the carbonized silk cloth prepared in Example 1, and (c) and (d) show The SEM image of the carbonized silk cloth obtained in Example 2;
图2显示本发明实施例1制得的碳化蚕丝布的氮元素的XPS图;Fig. 2 shows the XPS diagram of nitrogen element of the carbonized silk cloth obtained in Example 1 of the present invention;
图3显示本发明实施例1制得的碳化蚕丝布的氧元素的XPS图;Fig. 3 shows the XPS diagram of oxygen element of the carbonized silk cloth obtained in Example 1 of the present invention;
图4显示本发明实施例1制得的碳化蚕丝布在沉积3mAh cm-2锂金属后的SEM图;Fig. 4 shows the SEM image of the carbonized silk cloth prepared in Example 1 of the present invention after depositing 3mAh cm -2 lithium metal;
图5显示本发明实施例1制得的碳化蚕丝布的库伦效率图;Fig. 5 shows the Coulomb efficiency diagram of the carbonized silk cloth obtained in Example 1 of the present invention;
图6显示本发明实施例1制得的碳化蚕丝布复合锂电极组装的对称电池循环稳定性测试结果;Fig. 6 shows the cycle stability test result of the symmetrical battery assembled with the carbonized silk cloth composite lithium electrode prepared in Example 1 of the present invention;
图7显示本发明实施例1中以碳化蚕丝布为集流体的硫正极的SEM图,其中(a)为正视图,(b)为截面图;Fig. 7 shows the SEM image of the sulfur positive electrode with carbonized silk cloth as the current collector in Example 1 of the present invention, wherein (a) is a front view, and (b) is a cross-sectional view;
图8显示本发明实施例1中装配的锂硫电池的循环性能图;FIG. 8 shows the cycle performance diagram of the lithium-sulfur battery assembled in Example 1 of the present invention;
图9显示本发明实施例1中以碳化蚕丝布为集流体的锂硫电池在较高负载下的循环性能图;Fig. 9 shows the cycle performance diagram of the lithium-sulfur battery using carbonized silk cloth as the current collector under higher load in Example 1 of the present invention;
图10显示本发明实施例1中以碳化蚕丝布为集流体的柔性软包锂硫电池的循环性能图;Figure 10 shows the cycle performance diagram of the flexible soft-pack lithium-sulfur battery using carbonized silk cloth as the current collector in Example 1 of the present invention;
图11显示本发明实施例1中以碳化蚕丝布为集流体的柔性软包锂硫电池的循环性能图。FIG. 11 shows the cycle performance diagram of the flexible soft-pack lithium-sulfur battery using carbonized silk cloth as the current collector in Example 1 of the present invention.
具体实施方式Detailed ways
为了使本发明所解决的技术问题、所采用的技术方案及所获得的有益效果更加清楚明白,以下结合附图及具体实施例对本发明进行进一步详细说明。应当理解,此处所描述的具体实施例仅仅用以解释本发明,并不用于限定本发明。In order to make the technical problems solved by the present invention, the technical solutions adopted and the beneficial effects obtained more clearly, the present invention will be further described in detail below with reference to the accompanying drawings and specific embodiments. It should be understood that the specific embodiments described herein are only used to explain the present invention, but not to limit the present invention.
本发明第一方面提供了一种柔性电极,该柔性电极包含碳化蚕丝织物和与该碳化蚕丝织物复合的电极活性材料。A first aspect of the present invention provides a flexible electrode comprising a carbonized silk fabric and an electrode active material compounded with the carbonized silk fabric.
本发明创新性地将碳化蚕丝织物作为基材与电极活性材料进行复合,利用碳化蚕丝织物的柔性和导电性制作成柔性电极。既可以与正极活性材料进行复合以制作柔性正极,也可以与负极活性材料进行符合以制作柔性负极。制得的柔性正极或柔性正极可以进一步用于制作柔性电池。本文所用的术语“复合”应以广泛的含义来理解,包括任何使碳化蚕丝织物与电极活性材料在电学上结合的方式。例如,下文所述的柔性锂负极通过沉积锂金属于碳化蚕丝织物上来制备,在这种情况下,通过沉积方式使碳化蚕丝织物与电极活性材料进行复合。又如,下文所述的柔性硫正极通过将正极活性材料与导电添加剂、粘结剂制备成正极浆料,然后将正极浆料涂覆于碳化蚕丝织物上来制备,在这种情况下,通过涂覆方式使碳化蚕丝织物与电极活性材料进行复合。The invention innovatively uses the carbonized silk fabric as a base material to compound the electrode active material, and utilizes the flexibility and conductivity of the carbonized silk fabric to make a flexible electrode. It can be compounded with positive active materials to make flexible positive electrodes, and can also be combined with negative active materials to make flexible negative electrodes. The prepared flexible positive electrode or flexible positive electrode can be further used to fabricate a flexible battery. The term "composite" as used herein should be understood in a broad sense to include any means of electrically combining a carbonized silk fabric with an electrode active material. For example, the flexible lithium anodes described below are prepared by depositing lithium metal on carbonized silk fabrics, in which case the carbonized silk fabrics are composited with electrode active materials by deposition. For another example, the flexible sulfur positive electrode described below is prepared by preparing a positive electrode active material, a conductive additive and a binder into a positive electrode slurry, and then coating the positive electrode slurry on the carbonized silk fabric, in this case, by coating The carbonized silk fabric is compounded with the electrode active material by the coating method.
蚕丝是蚕在变为蚕蛾前的休眠期吐出来的,按蚕的品种分,蚕丝有桑蚕丝、柞蚕丝、蓖麻蚕丝和木薯蚕丝等,常用的是桑蚕丝和柞蚕丝。蚕丝是天然蛋白质纤维的一种,由外层的丝胶和内层的丝素(蚕丝蛋白)组成。蚕丝直径小、光滑、有光泽并具有弹性,用于织物时无需纺丝,只需两股合并然后加捻就可成为连续绳状长丝。蚕丝织物外观优雅、穿着舒适并具有美学价值,千百年来一直是高端服饰的材料。由于蚕丝织物富含碳元素,柔软轻薄,随着柔性电池、柔性可穿戴设备的兴起,蚕丝织物作为柔性导电材料的原料也引起了人们的极大兴趣。Silk is spit out by silkworms in the dormant period before becoming silkworm moths. According to the variety of silkworms, silks include mulberry silk, tussah silk, castor silk and cassava silk, etc. The commonly used ones are mulberry silk and tussah silk. Silk is a kind of natural protein fiber, which is composed of sericin in the outer layer and silk fibroin (fibroin) in the inner layer. The silk is small in diameter, smooth, shiny and elastic. It does not need to be spun when used in fabrics. It only requires two strands to be combined and then twisted to form a continuous rope-like filament. Elegant, comfortable and aesthetically pleasing, silk fabrics have been the material of high-end apparel for thousands of years. Because silk fabrics are rich in carbon elements, soft and thin, with the rise of flexible batteries and flexible wearable devices, silk fabrics have also attracted great interest as a raw material for flexible conductive materials.
本文所用的术语“蚕丝织物”既包括常见的蚕丝织物布料,也包括通过静电纺丝制备的再生丝素纤维。本文所用的术语“碳化蚕丝织物”是指对蚕丝织物进行高温热处理等处理后得到的柔性导电材料。The term "silk fabric" as used herein includes both common silk fabric cloths and regenerated silk fibroin fibers prepared by electrospinning. The term "carbonized silk fabric" as used herein refers to a flexible conductive material obtained by subjecting the silk fabric to high temperature heat treatment and the like.
通常,碳化蚕丝织物通过以下方法制得:在惰性气体保护下,将蚕丝织物在第一温度下进行脱水处理,在第二温度下进行环化处理,并在第三温度下进行碳化处理,得到所述炭化蚕丝织物。Usually, the carbonized silk fabric is prepared by the following method: under the protection of an inert gas, the silk fabric is subjected to dehydration treatment at a first temperature, cyclization treatment at a second temperature, and carbonization treatment at a third temperature to obtain The carbonized silk fabric.
不受理论的限制,据信蚕丝织物中的蚕丝蛋白在梯度升温加热后,相邻的肽链之间发生分子内脱水,继而发生芳香化或者环化形成六角形碳环,最后甚至生成高度有序的石墨结构。Without being limited by theory, it is believed that after the fibroin in silk fabrics is heated by gradient heating, intramolecular dehydration occurs between adjacent peptide chains, followed by aromatization or cyclization to form hexagonal carbocyclic rings, and finally even highly ordered graphite structure.
可以理解,第一温度是适于使蚕丝织物脱水的温度,第二温度是使蚕丝织物中的蛋白质中的氨基和羧基基团发生环化反应而形成氮氧掺杂结构的温度,第三温度是适于使蚕丝织物发生碳化的温度。可以理解,第二温度高于第一温度,第三温度高于第二温度,在第一温度、第二温度和第三温度下处理合适的时间,并且从第一温度转变到第二温度和从第二温度转变到第三温度是以合适的升温速率转变。It can be understood that the first temperature is the temperature suitable for dehydrating the silk fabric, the second temperature is the temperature at which the amino and carboxyl groups in the protein in the silk fabric undergo cyclization reaction to form a nitrogen-oxygen doped structure, and the third temperature It is the temperature suitable for carbonization of silk fabrics. It can be understood that the second temperature is higher than the first temperature, the third temperature is higher than the second temperature, and the first temperature, the second temperature and the third temperature are processed for the appropriate time, and the transition from the first temperature to the second temperature and The transition from the second temperature to the third temperature is at a suitable ramp rate.
在本发明的一些实施方案中,碳化蚕丝织物通过以下方法制得:在惰性气体保护下,将蚕丝织物在100℃-200℃之间的第一温度下进行脱水处理1-2h,然后在300℃-400℃之间的第二温度下进行环化处理2-3h,然后在950℃-1100℃之间的第三温度下进行碳化处理1-2h,蚕丝织物升温到第一温度、第二温度和第三温度的升温速率独立地为2℃-10℃/min。In some embodiments of the present invention, the carbonized silk fabric is prepared by the following method: under the protection of inert gas, the silk fabric is subjected to a dehydration treatment at a first temperature between 100 ° C and 200 ° C for 1-2 h, and then at 300 ° C. The cyclization treatment is carried out at the second temperature between ℃-400℃ for 2-3h, and then the carbonization treatment is carried out at the third temperature between 950℃-1100℃ for 1-2h, and the silk fabric is heated to the first temperature, the second temperature The ramp rates of the temperature and the third temperature are independently 2°C to 10°C/min.
上述惰性气体为化学化工反应中常用的惰性气体,例如氩气、氖气、氮气或者它们的混合物。另外,在惰性气体中也可混入适量的氢气或者氨气,即反应气氛可以为惰性气体和氢气或者氨气的混合气体。混入的氢气和氩气具有还原性,可以减少最终碳化蚕丝织物的氧掺杂含量,提高其导电性。The above-mentioned inert gas is an inert gas commonly used in chemical and chemical reactions, such as argon, neon, nitrogen or their mixtures. In addition, an appropriate amount of hydrogen or ammonia can also be mixed into the inert gas, that is, the reaction atmosphere can be a mixed gas of an inert gas and hydrogen or ammonia. The mixed hydrogen and argon have reducing properties, which can reduce the oxygen doping content of the final carbonized silk fabric and improve its electrical conductivity.
在上述碳化方法中,在使用大块的蚕丝织物(例如蚕丝布)的情况下,通常将其裁剪为大小合适的方块后进行处理。并且,通常优选地,可以将蚕丝织物先用去离子水和无水乙醇各超声15-20min,然后60℃烘干,以供后续进行处理。In the above-mentioned carbonization method, when a large piece of silk fabric (eg, silk cloth) is used, it is usually cut into squares of suitable size and then processed. And, generally preferably, the silk fabric can be ultrasonicated for 15-20 min each with deionized water and absolute ethanol, and then dried at 60° C. for subsequent treatment.
本发明对蚕丝织物的材质没有具体的限制,不过通常优选纯桑蚕丝或柞蚕丝,纺织方式包括双绉、素绉、鬼绉和电力纺,厚度为8-46姆米,进一步优选地,蚕丝织物为22姆米的素绉桑蚕丝面料。The present invention has no specific limitation on the material of the silk fabric, but usually pure mulberry silk or tussah silk is preferred. The fabric is plain crepe mulberry silk of 22 mm.
在本发明的柔性电极的一些实施方案中,电极活性材料为负极活性材料。在电池领域中,负极活性材料的非限制性实例包括锂金属、硅、石墨、金属氧化物等。对于硅、石墨、金属氧化物负极活性材料,通常可以将其与粘结剂、导电添加剂按照一定的比例(例如(8-9):1:1)在适量的溶剂中均匀混合,得到负极浆料,然后将负极浆料涂覆在碳化蚕丝织物上,真空干燥除去溶剂,得到复合好的柔性负极。In some embodiments of the flexible electrodes of the present invention, the electrode active material is a negative electrode active material. In the battery field, non-limiting examples of negative electrode active materials include lithium metal, silicon, graphite, metal oxides, and the like. For silicon, graphite, and metal oxide negative electrode active materials, it can usually be uniformly mixed with a binder and conductive additives in a certain ratio (eg (8-9):1:1) in an appropriate amount of solvent to obtain a negative electrode slurry Then, the negative electrode slurry is coated on the carbonized silk fabric, and the solvent is removed by vacuum drying to obtain a composite flexible negative electrode.
进一步地,在一个优选的实施方案中,负极活性材料为锂金属,柔性电极相应地为柔性锂负极。该柔性柔性锂负极通过以下方法制备:将碳化蚕丝织物裁剪为大小合适的碳化蚕丝织物极片,与锂金属电极相匹配,组装为半电池;在电流大小恒定的条件下,将锂金属定量沉积到碳化蚕丝织物极片上;然后取出沉积有锂金属的碳化蚕丝织物极片,用有机溶剂冲洗,干燥,得到柔性锂负极。干燥的方式可以是自然晾干,或者低温烘干,或者其他合适的干燥方式。通常,设定电流大小在0.1-1mA cm-2的范围内,锂金属的沉积量在1-20mAhcm-2的范围内。所用的有机溶剂可以例如为碳酸二甲酯(DMC)、1,3-二氧戊环(DOL)或二甲氧基乙烷(DME)。应该指出的是,尽管这里采用电沉积法来将锂金属与碳化蚕丝织物复合制备柔性锂负极,但是还可以采用本领域公知的其他复合方法如锂热熔法来制备柔性锂负极。Further, in a preferred embodiment, the negative electrode active material is lithium metal, and the flexible electrode is correspondingly a flexible lithium negative electrode. The flexible and flexible lithium negative electrode is prepared by the following methods: cutting carbonized silk fabric into carbonized silk fabric pole pieces of suitable size, matching with lithium metal electrodes, and assembling a half-cell; under the condition of constant current, quantitatively depositing lithium metal onto the carbonized silk fabric pole piece; then take out the carbonized silk fabric pole piece deposited with lithium metal, rinse with an organic solvent, and dry to obtain a flexible lithium negative electrode. The drying method can be natural drying, low temperature drying, or other suitable drying methods. Usually, the current size is set in the range of 0.1-1 mA cm -2 , and the deposition amount of lithium metal is in the range of 1-20 mAh cm- 2 . The organic solvent used can be, for example, dimethyl carbonate (DMC), 1,3-dioxolane (DOL) or dimethoxyethane (DME). It should be pointed out that although the electrodeposition method is used to composite lithium metal and carbonized silk fabric to prepare flexible lithium negative electrode, other composite methods known in the art such as lithium hot melt method can also be used to prepare flexible lithium negative electrode.
在本发明的柔性电极的另一些实施方案中,电极活性材料为正极活性材料。在电池领域中,正极活性材料的非限制性实例通常包括镍钴锰三元材料(NCM)、钴酸锂(LCO)、磷酸铁锂(LFP)、镍钴铝三元材料(NCA)、锰酸锂(LMO)和镍酸锂(LNO)等;而在金属硫电池如锂硫电池中,正极活性材料为包含硫元素的正极活性材料,例如单质硫、硫复合物(如硫碳、硫硒或硫碲复合物等)或者多硫化合物(如Li2S8、Li2S6等)。In other embodiments of the flexible electrodes of the present invention, the electrode active material is a positive electrode active material. In the battery field, non-limiting examples of positive active materials generally include nickel cobalt manganese ternary material (NCM), lithium cobalt oxide (LCO), lithium iron phosphate (LFP), nickel cobalt aluminum ternary material (NCA), manganese Lithium oxide (LMO) and lithium nickelate (LNO), etc.; and in metal-sulfur batteries such as lithium-sulfur batteries, the positive electrode active material is a positive electrode active material containing sulfur, such as elemental sulfur, sulfur composites (such as sulfur carbon, sulfur selenium or sulfur-tellurium complexes, etc.) or polysulfide compounds (such as Li 2 S 8 , Li 2 S 6 , etc.).
进一步地,在一些优选的实施方案中,电极活性材料为正极活性材料,该正极活性材料为镍钴锰三元材料(NCM)、钴酸锂(LCO)和磷酸铁锂(LFP)中的一种或多种。该柔性电极通过以下方法制备:将该正极活性材料与导电添加剂、粘结剂按照(4-9):(1-2):1的质量比在适量的溶剂中混合均匀,得到正极浆料;然后将所得的正极浆料均匀涂覆于该碳化蚕丝织物上,在60℃-80℃下真空干燥12-16h以去除溶剂,得到该柔性电极。所用的导电添加剂为乙炔黑、科琴黑、Super P、Super C45、碳纳米管、石墨烯中的一种或多种,粘结剂为水系粘结剂(例如PAA、LA123、丝胶蛋白)或者有机溶剂系粘结剂(例如PVDF)。Further, in some preferred embodiments, the electrode active material is a positive electrode active material, and the positive electrode active material is one of nickel-cobalt-manganese ternary material (NCM), lithium cobalt oxide (LCO) and lithium iron phosphate (LFP). one or more. The flexible electrode is prepared by the following method: the positive electrode active material, the conductive additive and the binder are uniformly mixed in an appropriate amount of solvent according to the mass ratio of (4-9):(1-2):1 to obtain a positive electrode slurry; Then, the obtained positive electrode slurry is uniformly coated on the carbonized silk fabric, and vacuum-dried at 60° C.-80° C. for 12-16 hours to remove the solvent to obtain the flexible electrode. The conductive additives used are one or more of acetylene black, Ketjen black, Super P, Super C45, carbon nanotubes, and graphene, and the binder is a water-based binder (such as PAA, LA123, sericin) Or an organic solvent based binder (eg PVDF).
另外进一步地,在另一些优选的实施方案中,电极活性材料为正极活性材料,正极活性材料包含硫元素,柔性电极相应地为柔性硫正极。简单而言,对于单质硫或者硫复合物,可以将其与导电添加剂、粘合剂在适量的溶剂中混合均匀,得到正极浆料,然后将所得的正极浆料均匀涂覆于碳化蚕丝织物上,真空干燥去除溶剂得到柔性硫电极;对于多硫化物,可以将其溶解于电解液中,再将电解液滴到碳化蚕丝织物上得到柔性硫电极。Further, in some other preferred embodiments, the electrode active material is a positive electrode active material, the positive electrode active material contains sulfur element, and the flexible electrode is correspondingly a flexible sulfur positive electrode. In simple terms, for elemental sulfur or sulfur complex, it can be mixed with conductive additives and binders in an appropriate amount of solvent to obtain a positive electrode slurry, and then the obtained positive electrode slurry can be uniformly coated on the carbonized silk fabric. , and vacuum drying to remove the solvent to obtain a flexible sulfur electrode; for polysulfide, it can be dissolved in the electrolyte, and then the electrolyte can be dropped onto the carbonized silk fabric to obtain a flexible sulfur electrode.
在一个以硫单质制备柔性硫正极的优选实施方案中,该柔性硫正极通过以下方法制备:将硫粉与导电添加剂按照(2-3):1的质量比混合并充分研磨,将研磨好的混合物在惰性气体保护下在150-160℃下进行水热反应12-16h,得到硫复合物;将所得的硫复合物和粘结剂按照(8-9):1的质量比在适量的溶剂中充分混合,得到正极浆料;然后将所得的正极浆料涂覆于该碳化蚕丝织物上,在60℃-80℃下真空干燥12-16h以去除溶剂,得到柔性硫正极。所用的导电添加剂为乙炔黑、科琴黑、Super P、Super C45、碳纳米管、石墨烯中的一种或多种,粘结剂为水系粘结剂或者有机溶剂系粘结剂。In a preferred embodiment for preparing a flexible sulfur positive electrode with simple sulfur, the flexible sulfur positive electrode is prepared by the following method: mixing sulfur powder and conductive additive in a mass ratio of (2-3):1 and fully grinding, and grinding the ground The mixture is subjected to a hydrothermal reaction at 150-160 ° C for 12-16 h under the protection of inert gas to obtain a sulfur compound; the obtained sulfur compound and binder are mixed in an appropriate amount of solvent according to the mass ratio of (8-9): 1 Then, the obtained positive electrode slurry is coated on the carbonized silk fabric, and vacuum-dried at 60°C-80°C for 12-16 hours to remove the solvent to obtain a flexible sulfur positive electrode. The conductive additive used is one or more of acetylene black, Ketjen black, Super P, Super C45, carbon nanotube, and graphene, and the binder is a water-based binder or an organic solvent-based binder.
在上述的柔性电极制备中使用的溶剂包括有机溶剂和水,具体的溶剂以使用的粘结剂为准。例如,粘结剂使用有机溶剂系粘结剂(例如PVDF)时,溶剂为有机溶剂;粘结剂使用水系粘结剂(例如LA123)时,溶剂为水。The solvents used in the preparation of the above-mentioned flexible electrodes include organic solvents and water, and the specific solvents are subject to the binder used. For example, when an organic solvent-based binder (eg PVDF) is used as the binder, the solvent is an organic solvent; when a water-based binder (eg, LA123) is used as the binder, the solvent is water.
本发明第二方面提供了一种柔性电池,其包括电极、隔膜和电解液,该电极包括正极和负极,该隔膜位于正极和负极之间,该电极包括根据本发明第一方面的柔性电极。A second aspect of the present invention provides a flexible battery, which includes an electrode, a separator and an electrolyte, the electrode includes a positive electrode and a negative electrode, the separator is located between the positive electrode and the negative electrode, and the electrode includes the flexible electrode according to the first aspect of the present invention.
如上文所述,本发明的柔性电极包括柔性正极和柔性负极,柔性正极的一个优选实例为柔性硫正极,柔性负极的一个优选实例为柔性锂负极。在本发明的一些实施方案中,本发明的柔性电池包含本发明的柔性正极和电池领域的其他柔性负极。在本发明的另一些实施方案中,本发明的柔性电池包含本发明的柔性负极和电池领域的其他柔性正极。在本发明的又一些实施方案中,本发明的柔性电池包含本发明的柔性负极和本发明的柔性正极。应该指出的是,本发明的创新在于柔性电极和包含柔性电极的柔性电池,柔性电池中的隔膜和电解液可以采用电池领域或者更具体地柔性电池领域常用的隔膜和电解液,在本文中不作赘述。As described above, the flexible electrode of the present invention includes a flexible positive electrode and a flexible negative electrode, a preferred example of the flexible positive electrode is a flexible sulfur positive electrode, and a preferred example of the flexible negative electrode is a flexible lithium negative electrode. In some embodiments of the present invention, the flexible battery of the present invention comprises the flexible positive electrode of the present invention and other flexible negative electrodes in the battery field. In other embodiments of the present invention, the flexible battery of the present invention comprises the flexible negative electrode of the present invention and other flexible positive electrodes in the battery field. In yet other embodiments of the present invention, the flexible battery of the present invention comprises a flexible negative electrode of the present invention and a flexible positive electrode of the present invention. It should be pointed out that the innovation of the present invention lies in the flexible electrodes and the flexible batteries comprising the flexible electrodes. The separators and electrolytes in the flexible batteries can adopt the separators and electrolytes commonly used in the battery field or more specifically in the field of flexible batteries, which are not described in this paper. Repeat.
在本发明的柔性电池的一些优选实施方案中,负极采用本发明第一方面的柔性锂负极,该柔性电池相应地为柔性锂电池。在本发明的柔性电池的另一些优选实施方案中,正极采用本发明第一方面的柔性硫正极,该柔性电池相应地为柔性硫电池。在本发明的柔性电池的又一些优选实施方案中,负极采用本发明第一方面的柔性锂负极,正极采用本发明第一方面的柔性硫正极,该柔性电池相应地为柔性锂硫电池。In some preferred embodiments of the flexible battery of the present invention, the negative electrode adopts the flexible lithium negative electrode of the first aspect of the present invention, and the flexible battery is correspondingly a flexible lithium battery. In other preferred embodiments of the flexible battery of the present invention, the positive electrode adopts the flexible sulfur positive electrode of the first aspect of the present invention, and the flexible battery is correspondingly a flexible sulfur battery. In further preferred embodiments of the flexible battery of the present invention, the negative electrode adopts the flexible lithium negative electrode of the first aspect of the present invention, and the positive electrode adopts the flexible sulfur positive electrode of the first aspect of the present invention, and the flexible battery is correspondingly a flexible lithium-sulfur battery.
以下通过具体实施例对本发明作进一步的具体说明。应该指出的是,这些实施例旨在进行举例说明本发明,并不意在以任何方式限制本发明的范围。The present invention will be further described in detail below through specific embodiments. It should be noted that these examples are intended to illustrate the invention and are not intended to limit the scope of the invention in any way.
实施例1Example 1
(1)碳化蚕丝布的制备与表征(1) Preparation and characterization of carbonized silk cloth
将22姆米的素绉桑蚕丝布裁剪为4cm*6cm的方块,用去离子水和无水乙醇各超声预处理15min,然后60℃烘干备用。Cut the 22 mm plain crepe mulberry silk cloth into 4cm*6cm squares, pre-treat with deionized water and absolute ethanol by ultrasonic for 15min each, and then dry at 60°C for later use.
将经预处理的蚕丝布置于管式炉中,在氩气的保护下,梯度升温进行碳化,控温程序为:室温升温至150℃(升温速率10℃/min),恒温1h;150℃升温至350℃(升温速率2℃/min),恒温3h;350℃升温至950℃(升温速率3℃/min),恒温1h,制得碳化蚕丝布。The pretreated silk was placed in a tube furnace, and under the protection of argon, the carbonization was carried out by gradient heating. To 350°C (
制得的碳化蚕丝布的SEM形貌图见图1(a)和(b),由图可见碳化后的蚕丝布纤维结构完整,分布均匀,有助于良好导电性。The SEM images of the prepared carbonized silk cloth are shown in Figures 1(a) and (b). It can be seen from the figures that the fiber structure of the carbonized silk cloth is complete and uniform, which contributes to good electrical conductivity.
制得的碳化蚕丝布的氮元素的XPS图见图2,可见碳化蚕丝布富含丰富的氮掺杂结构,用于柔性硫正极时有助于吸附多硫化物,抑制多硫化物在硫电池隔膜上的穿梭效应,同时也使碳化蚕丝布具有良好的亲锂性,用于锂负极时可以抑制锂枝晶的产生。The XPS diagram of nitrogen element of the prepared carbonized silk cloth is shown in Figure 2. It can be seen that the carbonized silk cloth is rich in nitrogen-doped structure, which is helpful for the adsorption of polysulfides when used in a flexible sulfur cathode, and inhibits the effect of polysulfides in sulfur batteries. The shuttle effect on the separator also makes the carbonized silk cloth have good lithophilicity, which can inhibit the generation of lithium dendrites when used in the lithium negative electrode.
制得的碳化蚕丝布的氧元素的XPS图见图3,可见富含丰富的氧掺杂结构,用于柔性硫正极时有助于吸附多硫化物,抑制锂硫电池中多硫化物的“穿梭效应”。The XPS diagram of the oxygen element of the prepared carbonized silk cloth is shown in Figure 3. It can be seen that the oxygen-rich doped structure is used for the flexible sulfur cathode, which is helpful for the adsorption of polysulfides and inhibits the "polysulfide" in lithium-sulfur batteries. Shuttle Effect".
(2)柔性锂负极的制备与表征(2) Preparation and characterization of flexible lithium anode
将以上制得的碳化蚕丝布裁剪为大小合适的极片,与锂金属电极(天津中能锂业)相匹配,在手套箱中组装为半电池。采用NewareCT2001A电池测试系统,在电流密度为1mAcm-2的条件下,定量沉积1-20mAh cm-2锂金属到碳化蚕丝布上。结束后,在手套箱中将电池拆开,取出沉积有锂金属的碳化蚕丝布电极,用二甲氧基乙烷(DME)冲洗3次,自然晾干,得到柔性锂负极。The carbonized silk cloth prepared above was cut into pole pieces of suitable size, matched with lithium metal electrodes (Tianjin Zhongneng Lithium Industry), and assembled into a half-cell in a glove box. Using the NewareCT2001A battery test system, 1-20mAh cm -2 lithium metal was quantitatively deposited on the carbonized silk cloth under the condition of a current density of 1mAcm -2 . After the end, the battery was disassembled in the glove box, and the carbonized silk cloth electrode deposited with lithium metal was taken out, rinsed three times with dimethoxyethane (DME), and air-dried to obtain a flexible lithium negative electrode.
对其中沉积了3mAh cm-2锂金属的碳化蚕丝布复合锂负极进行SEM表征,结果见图4。与图1对比可以看出,锂金属均匀包覆在碳化蚕丝布纤维表面,这是因为碳化蚕丝布存在丰富的氮掺杂结构,具有良好的亲锂性,能够引导锂金属均匀成核,从而抑制锂枝晶的产生。The carbonized silk cloth composite lithium anode with 3 mAh cm -2 lithium metal deposited therein was characterized by SEM, and the results are shown in Figure 4. Compared with Fig. 1, it can be seen that lithium metal is evenly coated on the surface of carbonized silk cloth fibers. This is because carbonized silk cloth has a rich nitrogen-doped structure, which has good lithophilicity and can guide lithium metal to nucleate uniformly, thereby Inhibit the formation of lithium dendrites.
将未沉积锂的碳化蚕丝布与锂金属匹配,组装扣式半电池,进行库伦效率测试,对照样为铜箔Cu(常用负极集流体,二维材料)、碳毡CF(三维材料,不含氮氧掺杂,类似碳布),结果见图5。从图中可以看出,碳化蚕丝布库伦效率明显优于碳毡(CF)和铜箔(Cu),循环300次后,平均库伦效率高达99.45%,所以基于碳化蚕丝布制备的柔性锂负极能够减小锂的损耗,改善电池的循环稳定性。The carbonized silk cloth without lithium deposition was matched with lithium metal, the button-type half-cell was assembled, and the Coulomb efficiency test was carried out. Nitrogen-oxygen doping, similar to carbon cloth), the results are shown in Figure 5. It can be seen from the figure that the coulombic efficiency of carbonized silk cloth is obviously better than that of carbon felt (CF) and copper foil (Cu). Reduce the loss of lithium and improve the cycle stability of the battery.
用其中沉积了10mAh cm-2锂金属的碳化蚕丝布复合锂负极组装对称电池,进行循环稳定性测试,对照样依然为铜箔(Cu)和碳毡(CF),两者也都沉积了10mAh cm-2锂金属,结果见图6。从图中可以看出,在2mA cm-2-2mAh cm-2的条件下,碳化蚕丝布复合锂负极组装的对称电池能够稳定循环550h,表现出优异的循环稳定性,而铜箔(Cu)和碳毡(CF)复合锂负极组装的对称电池只能分别稳定循环大约300-340h,这是因为碳化蚕丝布的三维结构可以减小局部电流密度,丰富的氮掺杂结构可以引导锂金属的均匀成核,从而抑制了锂枝晶的生长,提高了电池的循环稳定性。A symmetrical battery was assembled with a carbonized silk cloth composite lithium negative electrode with 10mAh cm -2 of lithium metal deposited in it, and the cycle stability test was carried out. The control samples were still copper foil (Cu) and carbon felt (CF), both of which also deposited 10mAh. cm -2 Li metal, the results are shown in Figure 6. It can be seen from the figure that under the condition of 2mA cm -2 -2mAh cm -2 , the symmetric battery assembled with carbonized silk cloth composite lithium anode can stably cycle for 550h, showing excellent cycle stability, while copper foil (Cu) The symmetric battery assembled with carbon felt (CF) composite lithium anode can only cycle stably for about 300-340 h, respectively, because the three-dimensional structure of carbonized silk cloth can reduce the local current density, and the abundant nitrogen-doped structure can guide the lithium metal Uniform nucleation, thereby inhibiting the growth of lithium dendrites and improving the cycling stability of the battery.
(3)柔性硫正极的制备与表征(3) Preparation and characterization of flexible sulfur cathode
将硫粉与科琴黑按照质量比3:1混合,进行充分研磨。然后将研磨好的混合物置于水热反应釜中,在氩气保护下,155℃恒温16h,得到硫碳复合物。以水为溶剂,丝胶蛋白为粘结剂,将硫碳复合物和粘结剂按照质量比9:1充分混合,得到水系电极浆料。将该电极浆料涂覆于以上制得的碳化蚕丝布上,并60℃真空干燥16h,除去溶剂,得到柔性硫正极,其SEM形貌图见图7。从图中可以看出,以碳化蚕丝布为集流体,浆料能够充分渗透到碳化蚕丝布的三维结构中,有利于活性物质的均匀分布,当提高硫负载时,活性材料不易脱落,极片不容易掉粉。Mix sulfur powder and Ketjen black in a mass ratio of 3:1, and grind thoroughly. Then, the ground mixture was placed in a hydrothermal reactor, and under the protection of argon, the temperature was kept at 155 °C for 16 h to obtain a sulfur-carbon composite. Using water as a solvent and sericin as a binder, the sulfur-carbon composite and the binder are fully mixed according to a mass ratio of 9:1 to obtain an aqueous electrode slurry. The electrode slurry was coated on the carbonized silk cloth prepared above, and vacuum-dried at 60° C. for 16 h to remove the solvent to obtain a flexible sulfur positive electrode. The SEM morphology is shown in FIG. 7 . It can be seen from the figure that with carbonized silk cloth as the current collector, the slurry can fully penetrate into the three-dimensional structure of carbonized silk cloth, which is conducive to the uniform distribution of active substances. Not easy to powder.
以同样的方法,制备了以碳毡CF(三维材料,不含氮氧掺杂,类似碳布)和石墨片GF(二维材料)为集流体的硫正极作为对比样。In the same way, a sulfur cathode with carbon felt CF (three-dimensional material, no nitrogen and oxygen doping, similar to carbon cloth) and graphite sheet GF (two-dimensional material) as current collectors was prepared as a comparison sample.
将制得的柔性硫正极和对比硫正极分别在手套箱中与锂金属匹配,组装为半电池,进行电化学性能测试,电池循环性能见图8和图9。图8显示基于碳化蚕丝布制备的柔性硫正极,在硫负载为2.55mg cm-2的条件下,循环200次,比容量为784mAh g-1,容量保持率79.5%,平均库伦效率高达98.95%,性能明显优于作为对照样的碳毡(CF)和石墨片(GF)。这是因为碳化蚕丝布的三维结构可以缓冲硫体积变化引起的应力,丰富的氮氧掺杂结构可以吸附多硫化物,抑制多硫化物在硫电池隔膜上的穿梭效应,锂硫电池的循环性能得以改善。图9显示当提高硫负载时,以碳化蚕丝布为集流体的锂硫电池依然能稳定循环,硫负载为6mg cm-2时,面容量可达5.4mAh cm-2,表明基于碳化蚕丝布制备的柔性硫正极适用于制作高面容量的锂硫电池。The prepared flexible sulfur cathode and comparative sulfur cathode were matched with lithium metal in a glove box, respectively, and assembled into half-cells for electrochemical performance tests. The battery cycle performance is shown in Figures 8 and 9. Figure 8 shows the flexible sulfur cathode prepared based on carbonized silk cloth, under the condition of sulfur loading of 2.55 mg cm -2 , after 200 cycles, the specific capacity is 784 mAh g -1 , the capacity retention rate is 79.5%, and the average Coulombic efficiency is as high as 98.95% , the performance is significantly better than that of carbon felt (CF) and graphite sheet (GF) as the control. This is because the three-dimensional structure of carbonized silk cloth can buffer the stress caused by the volume change of sulfur, and the rich nitrogen-oxygen doped structure can adsorb polysulfides, inhibit the shuttle effect of polysulfides on the sulfur battery separator, and the cycle performance of lithium-sulfur batteries. be improved. Figure 9 shows that when the sulfur loading is increased, the lithium - sulfur battery with carbonized silk cloth as the current collector can still cycle stably. The flexible sulfur cathode is suitable for fabricating high areal capacity lithium-sulfur batteries.
(4)柔性锂硫电池的制备(4) Preparation of flexible lithium-sulfur batteries
将上述制备的柔性锂负极和柔性硫正极分别裁剪为2cm*4cm的大小。在手套箱中,将两种电极相匹配,使用Celgard公司的聚丙烯隔膜以及常规的锂硫电解液(成分:1.0MLiTFSI/DME:DOL=1:1Vol%,添加2.0%LiNO3,公司:苏州多多化学试剂有限公司),以铝塑膜作为封装,组装软包电池,得到基于碳化蚕丝布的柔性良好的锂硫电池。The above-prepared flexible lithium anode and flexible sulfur cathode were cut to the size of 2cm*4cm, respectively. In the glove box, the two electrodes were matched, using Celgard's polypropylene separator and conventional lithium-sulfur electrolyte (composition: 1.0M LiTFSI/DME: DOL=1:1 Vol%, adding 2.0% LiNO 3 , company: Suzhou Duoduo Chemical Reagent Co., Ltd.), using aluminum-plastic film as a package to assemble a soft-pack battery to obtain a flexible lithium-sulfur battery based on carbonized silk cloth.
图10为基于碳化蚕丝布组装的柔性软包锂硫全电池的循环性能图,电池硫负载为2.0mg cm-2,测试的电流大小为1mA cm-2,由图可知,该软包电池循环稳定性良好,前150次循环平均库伦效率高达98.9%,循环150次后,在曲率半径为5mm的条件下弯折1000次,电池容量仅略微衰减,依旧能稳定循环,库伦效率基本保持不变。Figure 10 shows the cycle performance diagram of the flexible soft - pack lithium - sulfur full battery assembled based on carbonized silk cloth. Good stability, the average Coulomb efficiency of the first 150 cycles is as high as 98.9%, after 150 cycles, after 1000 cycles of bending under the condition of a curvature radius of 5mm, the battery capacity is only slightly attenuated, and it can still be cycled stably, and the Coulomb efficiency remains basically unchanged. .
图11也为基于碳化蚕丝布组装的柔性软包锂硫全电池的循环性能图,电池硫负载为2.0mg cm-2,测试的电流大小为0.5mA cm-2,循环50次后,在曲率半径为5mm的条件下弯折1000次,电池依然能够稳定循环,整体的平均库伦效率高达98.4%。Figure 11 is also a graph of the cycle performance of the flexible soft - packed lithium - sulfur full battery assembled based on carbonized silk cloth.
图10和图11均表明,基于碳化蚕丝布组装的柔性软包锂硫全电池的柔性以及循环稳定性优异,具有很好的应用前景。Both Figure 10 and Figure 11 show that the flexible soft-packed lithium-sulfur full battery assembled based on carbonized silk cloth has excellent flexibility and cycle stability, and has a good application prospect.
实施例2Example 2
(1)碳化蚕丝布的制备与表征(1) Preparation and characterization of carbonized silk cloth
将30姆米的素绉桑蚕丝布裁剪为4cm*6cm的方块,用去离子水和无水乙醇各超声预处理15min,然后60℃烘干备用。Cut 30 mm plain crepe mulberry silk cloth into squares of 4 cm*6 cm, pre-treated with deionized water and absolute ethanol by ultrasonic for 15 min each, and then dried at 60°C for use.
将经预处理的蚕丝布置于管式炉中,在氩气的保护下,梯度升温进行碳化,控温程序为:室温升温至200℃(升温速率5℃/min),恒温1h;200℃升温至400℃(升温速率3℃/min),恒温3h;400℃升温至1000℃(升温速率3℃/min),恒温1h,制得碳化蚕丝布。The pretreated silk was placed in a tube furnace, and under the protection of argon, the carbonization was carried out by gradient heating. To 400°C (
所得的碳化蚕丝布的SEM形貌图见图1(c)和(d),由图可见碳化后的蚕丝布纤维结构完整,分布均匀,有助于良好导电性。The SEM images of the obtained carbonized silk cloth are shown in Figures 1(c) and (d). It can be seen from the figures that the fibers of the carbonized silk cloth are complete in structure and uniform in distribution, which contributes to good electrical conductivity.
(2)柔性锂负极的制备(2) Preparation of flexible lithium anode
将以上制得的碳化蚕丝布裁剪为大小合适的极片,与锂金属电极(天津中能锂业)相匹配,在手套箱中组装为半电池。采用NewareCT2001A电池测试系统,在电流密度为0.5mAcm-2的条件下,定量沉积3-20mAh cm-2锂金属到碳化蚕丝布上。结束后,在手套箱中将电池拆开,取出沉积有锂金属的碳化蚕丝布电极,用1,3-二氧戊环(DOL)冲洗3次,自然晾干,得到柔性锂负极。The carbonized silk cloth prepared above was cut into pole pieces of suitable size, matched with lithium metal electrodes (Tianjin Zhongneng Lithium Industry), and assembled into a half-cell in a glove box. Using the NewareCT2001A battery test system, under the condition of a current density of 0.5mAcm -2 , 3-20mAh cm -2 lithium metal was quantitatively deposited on the carbonized silk cloth. After the end, the battery was disassembled in the glove box, and the carbonized silk cloth electrode deposited with lithium metal was taken out, rinsed three times with 1,3-dioxolane (DOL), and dried naturally to obtain a flexible lithium negative electrode.
(3)柔性硫正极的制备(3) Preparation of flexible sulfur cathode
将硫粉与super P按照质量比3:1混合,进行充分研磨。然后将研磨好的混合物置于水热反应釜中,在氩气保护下,155℃恒温12h,得到硫碳复合物。以N-甲基吡咯烷酮(NMP)为溶剂,聚偏四氟乙烯(PVDF)为粘结剂,将硫碳复合物和粘结剂按照质量比9:1充分混合,得到有机溶剂系电极浆料。将该电极浆料涂覆于以上制得的碳化蚕丝布上,并80℃真空干燥12h,除去溶剂,得到柔性硫正极。Mix sulfur powder and super P in a mass ratio of 3:1, and grind them thoroughly. Then, the ground mixture was placed in a hydrothermal reactor, and under the protection of argon, the temperature was kept at 155 °C for 12 h to obtain a sulfur-carbon composite. Using N-methylpyrrolidone (NMP) as a solvent and polyvinylidene tetrafluoroethylene (PVDF) as a binder, the sulfur-carbon composite and the binder are fully mixed in a mass ratio of 9:1 to obtain an organic solvent-based electrode slurry . The electrode slurry was coated on the carbonized silk cloth prepared above, and vacuum-dried at 80° C. for 12 h to remove the solvent to obtain a flexible sulfur positive electrode.
(4)柔性锂硫电池的制备(4) Preparation of flexible lithium-sulfur batteries
将上述制备的柔性锂负极和柔性硫正极分别裁剪为2cm*4cm的大小。在手套箱中,将两种电极相匹配,使用Celgard公司的聚丙烯隔膜以及常规的锂硫电解液(成分:1.0MLiTFSI/DME:DOL=1:1Vol%,添加2.0%LiNO3,公司:苏州多多化学试剂有限公司),以铝塑膜作为封装,组装软包电池,得到基于碳化蚕丝布的柔性良好的锂硫电池。The above-prepared flexible lithium anode and flexible sulfur cathode were cut to the size of 2cm*4cm, respectively. In the glove box, the two electrodes were matched, using Celgard's polypropylene separator and conventional lithium-sulfur electrolyte (composition: 1.0M LiTFSI/DME: DOL=1:1 Vol%, adding 2.0% LiNO 3 , company: Suzhou Duoduo Chemical Reagent Co., Ltd.), using aluminum-plastic film as a package to assemble a soft-pack battery to obtain a flexible lithium-sulfur battery based on carbonized silk cloth.
实施例3Example 3
(1)碳化蚕丝布的制备(1) Preparation of carbonized silk cloth
将40姆米的素绉桑蚕丝布裁剪为4cm*6cm的方块,用去离子水和无水乙醇各超声预处理20min,然后60℃烘干备用。Cut 40 mm plain crepe mulberry silk cloth into squares of 4 cm*6 cm, pre-treat with deionized water and absolute ethanol for 20 min each by ultrasonic, and then dry at 60°C for use.
将经预处理的蚕丝布置于管式炉中,在氖气的保护下,梯度升温进行碳化,控温程序为:室温升温至200℃(升温速率5℃/min),恒温1h;200℃升温至350℃(升温速率5℃/min),恒温2h;350℃升温至950℃(升温速率5℃/min),恒温2h,制得碳化蚕丝布。The pretreated silk was placed in a tube furnace, and under the protection of neon gas, the carbonization was carried out by gradient heating. To 350°C (heating rate 5°C/min), constant temperature for 2h; 350°C to 950°C (heating rate 5°C/min), constant temperature for 2h, to obtain carbonized silk cloth.
(2)柔性锂负极的制备(2) Preparation of flexible lithium anode
将以上制得的碳化蚕丝布裁剪为大小合适的极片,与锂金属电极(天津中能锂业)相匹配,在手套箱中组装为半电池。采用NewareCT2001A电池测试系统,在电流密度为1mAcm-2的条件下,定量沉积5-15mAh cm-2锂金属到碳化蚕丝布上。结束后,在手套箱中将电池拆开,取出沉积有锂金属的碳化蚕丝布电极,用二甲氧基乙烷(DME)冲洗3次,自然晾干,得到柔性锂负极。The carbonized silk cloth prepared above was cut into pole pieces of suitable size, matched with lithium metal electrodes (Tianjin Zhongneng Lithium Industry), and assembled into a half-cell in a glove box. Using the NewareCT2001A battery test system, 5-15mAh cm -2 of lithium metal was quantitatively deposited on the carbonized silk cloth under the condition of a current density of 1 mAcm -2 . After the end, the battery was disassembled in the glove box, and the carbonized silk cloth electrode deposited with lithium metal was taken out, rinsed three times with dimethoxyethane (DME), and air-dried to obtain a flexible lithium negative electrode.
(3)柔性钴酸锂正极的制备(3) Preparation of flexible lithium cobalt oxide cathode
在适量的N-甲基吡咯烷酮(NMP)溶剂中,将LCO(钴酸锂)、super P(导电添加剂)、PVDF(粘结剂)按93:3:2的质量比进行充分混合,得到均匀的电极浆料。将电极浆料涂覆于以上制得的碳化蚕丝布上,80℃真空干燥12h,得到柔性钴酸锂正极。In an appropriate amount of N-methylpyrrolidone (NMP) solvent, LCO (lithium cobaltate), super P (conductive additive), PVDF (binder) are fully mixed in a mass ratio of 93:3:2 to obtain a uniform electrode paste. The electrode slurry was coated on the carbonized silk cloth prepared above, and vacuum-dried at 80° C. for 12 h to obtain a flexible lithium cobalt oxide positive electrode.
(4)柔性锂电池的制备(4) Preparation of flexible lithium battery
将以上制备的柔性锂负极和柔性钴酸锂正极分别裁剪成2cm*4cm的大小。在手套箱中,将两种电极相匹配,使用Celgard公司的聚丙烯隔膜以及常规的锂硫电解液(成分:1.0M LiTFSI/DME:DOL=1:1Vol%,添加2.0%LiNO3,公司:苏州多多化学试剂有限公司),以铝塑膜作为封装,组装软包电池,得到基于碳化蚕丝布的以柔性钴酸锂为正极材料的柔性锂电池。The flexible lithium negative electrode and flexible lithium cobalt oxide positive electrode prepared above were cut into sizes of 2cm*4cm, respectively. In a glove box, the two electrodes were matched using a polypropylene separator from Celgard and a conventional lithium-sulfur electrolyte (composition: 1.0M LiTFSI/DME:DOL=1:1 Vol% with 2.0% LiNO 3 added, Inc.: Suzhou Duoduo Chemical Reagent Co., Ltd.), using aluminum-plastic film as a package, assembling a soft pack battery, and obtaining a flexible lithium battery based on carbonized silk cloth with flexible lithium cobalt oxide as the positive electrode material.
实施例4Example 4
(1)碳化蚕丝布的制备(1) Preparation of carbonized silk cloth
将23姆米的鬼绉柞蚕丝布裁剪为4cm*6cm的方块,用去离子水和无水乙醇各超声20min,然后60℃烘干备用。Cut the 23-momi tussah silk cloth into 4cm*6cm squares, sonicate with deionized water and absolute ethanol for 20 minutes each, and then dry at 60°C for later use.
将经预处理的蚕丝布置于管式炉中,在氩氢混合气(氩气与氢气体积比为9:1)的保护下,梯度升温进行碳化,控温程序为:室温升温至100℃(升温速率5℃/min),恒温1h;100℃升温至300℃(升温速率5℃/min),恒温2h;300℃升温至1050℃(升温速率5℃/min),恒温1h,制得碳化蚕丝布。The pretreated silk was arranged in a tube furnace, and under the protection of an argon-hydrogen mixture (the volume ratio of argon and hydrogen was 9:1), the carbonization was carried out by gradient heating, and the temperature control program was: the temperature was raised to 100 ° C ( Heating rate of 5°C/min), constant temperature for 1h; 100°C to 300°C (heating rate of 5°C/min), constant temperature for 2h; 300°C to 1050°C (heating rate of 5°C/min), constant temperature for 1h, to obtain carbonization Silk cloth.
(2)柔性锂负极的制备(2) Preparation of flexible lithium anode
将以上制得的碳化蚕丝布裁剪为大小合适的极片,与锂金属电极(天津中能锂业)相匹配,在手套箱中组装为半电池。采用NewareCT2001A电池测试系统,在电流密度为0.8mAcm-2的条件下,定量沉积5-15mAh cm-2锂金属到碳化蚕丝布上。结束后,在手套箱中将电池拆开,取出沉积有锂金属的碳化蚕丝布电极,用二甲氧基乙烷(DME)冲洗3次,自然晾干,得到柔性锂负极。The carbonized silk cloth prepared above was cut into pole pieces of suitable size, matched with lithium metal electrodes (Tianjin Zhongneng Lithium Industry), and assembled into a half-cell in a glove box. Using NewareCT2001A battery test system, under the condition of current density of 0.8mAcm -2 , 5-15mAh cm -2 lithium metal was quantitatively deposited on carbonized silk cloth. After the end, the battery was disassembled in the glove box, and the carbonized silk cloth electrode deposited with lithium metal was taken out, rinsed three times with dimethoxyethane (DME), and air-dried to obtain a flexible lithium negative electrode.
(3)柔性镍钴锰正极的制备(3) Preparation of flexible nickel-cobalt-manganese cathode
在适量的N-甲基吡咯烷酮(NMP)溶剂中,将NCM(镍钴锰三元材料)、super P(导电添加剂)、PVDF(粘结剂)按80:10:10的质量比进行充分混合,得到均匀的电极浆料。将电极浆料涂覆于以上制得的碳化蚕丝布上,80℃真空干燥12h,得到柔性镍钴锰正极。In an appropriate amount of N-methylpyrrolidone (NMP) solvent, NCM (nickel-cobalt-manganese ternary material), super P (conductive additive), PVDF (binder) are thoroughly mixed in a mass ratio of 80:10:10 , to obtain a uniform electrode paste. The electrode slurry was coated on the carbonized silk cloth prepared above, and vacuum-dried at 80° C. for 12 h to obtain a flexible nickel-cobalt-manganese positive electrode.
(4)柔性锂电池的制备(4) Preparation of flexible lithium battery
将以上制备的柔性锂负极和柔性镍钴锰正极分别裁剪成2cm*4cm的大小。在手套箱中,将两种电极相匹配,使用Celgard公司的聚丙烯隔膜以及常规的锂硫电解液(成分:1.0M LiTFSI/DME:DOL=1:1Vol%,添加2.0%LiNO3,公司:苏州多多化学试剂有限公司),以铝塑膜作为封装,组装软包电池,得到基于碳化蚕丝布的以柔性镍钴锰为正极材料的柔性锂电池。The flexible lithium anode and flexible nickel-cobalt-manganese cathode prepared above were cut into sizes of 2cm*4cm, respectively. In a glove box, the two electrodes were matched using a polypropylene separator from Celgard and a conventional lithium-sulfur electrolyte (composition: 1.0M LiTFSI/DME:DOL=1:1 Vol% with 2.0% LiNO 3 added, Inc.: Suzhou Duoduo Chemical Reagent Co., Ltd.), used aluminum-plastic film as a package, assembled a soft-pack battery, and obtained a flexible lithium battery based on carbonized silk cloth with flexible nickel-cobalt-manganese as the positive electrode material.
实施例5Example 5
(1)碳化蚕丝布的制备(1) Preparation of carbonized silk cloth
将12姆米的鬼绉柞蚕丝布裁剪为4cm*6cm的方块,用去离子水和无水乙醇各超声15min,然后60℃烘干备用。Cut the 12-mummy tussah silk cloth into 4cm*6cm squares, sonicate with deionized water and absolute ethanol for 15min each, and then dry at 60°C for later use.
将经预处理的蚕丝布置于管式炉中,在氩氨混合气(氩气与氨气体积比为9:1)的保护下,梯度升温进行碳化,控温程序为:室温升温至150℃(升温速率5℃/min),恒温1.5h;150℃升温至400℃(升温速率3℃/min),恒温2.5h;400℃升温至1100℃(升温速率5℃/min),恒温1h,制得碳化蚕丝布。Arrange the pretreated silk in a tube furnace, and under the protection of argon-ammonia mixture (the volume ratio of argon and ammonia is 9:1), the carbonization is carried out by gradient heating, and the temperature control program is: the temperature is raised to 150 ° C (heating rate 5°C/min), constant temperature for 1.5h; heating from 150°C to 400°C (
(2)柔性锂负极的制备(2) Preparation of flexible lithium anode
将以上制得的碳化蚕丝布裁剪为大小合适的极片,与锂金属电极(天津中能锂业)相匹配,在手套箱中组装为半电池。采用NewareCT2001A电池测试系统,在电流密度为0.5mAcm-2的条件下,定量沉积3-10mAh cm-2锂金属到碳化蚕丝布上。结束后,在手套箱中将电池拆开,取出沉积有锂金属的碳化蚕丝布电极,用二甲氧基乙烷(DME)冲洗3次,自然晾干,得到柔性锂负极。The carbonized silk cloth prepared above was cut into pole pieces of suitable size, matched with lithium metal electrodes (Tianjin Zhongneng Lithium Industry), and assembled into a half-cell in a glove box. The NewareCT2001A battery test system was used to quantitatively deposit 3-10mAh cm -2 of lithium metal onto the carbonized silk cloth under the condition of a current density of 0.5mAcm -2 . After the end, the battery was disassembled in the glove box, and the carbonized silk cloth electrode deposited with lithium metal was taken out, rinsed three times with dimethoxyethane (DME), and air-dried to obtain a flexible lithium negative electrode.
(3)柔性磷酸铁锂正极的制备(3) Preparation of flexible lithium iron phosphate cathode
在适量的N-甲基吡咯烷酮(NMP)溶剂中,将LiFePO4(磷酸铁锂)、乙炔黑(导电添加剂)、PVDF(粘结剂)按70:15:15的质量比进行充分混合,得到均匀的电极浆料。将电极浆料涂覆于以上制得的碳化蚕丝布上,80℃真空干燥16h,得到柔性磷酸铁锂正极。In an appropriate amount of N-methylpyrrolidone (NMP) solvent, LiFePO 4 (lithium iron phosphate), acetylene black (conductive additive), and PVDF (binder) were thoroughly mixed in a mass ratio of 70:15:15 to obtain Homogeneous electrode paste. The electrode slurry was coated on the carbonized silk cloth prepared above, and vacuum-dried at 80° C. for 16 h to obtain a flexible lithium iron phosphate positive electrode.
(4)柔性锂电池的制备(4) Preparation of flexible lithium battery
将以上制备的柔性锂负极和柔性磷酸铁锂正极分别裁剪成2cm*4cm的大小。在手套箱中,将两种电极相匹配,使用Celgard公司的聚丙烯隔膜以及常规的锂硫电解液(成分:1.0M LiTFSI/DME:DOL=1:1Vol%,添加2.0%LiNO3,公司:苏州多多化学试剂有限公司),以铝塑膜作为封装,组装软包电池,得到基于碳化蚕丝布的以柔性磷酸铁锂为正极材料的柔性锂电池。The flexible lithium anode and flexible lithium iron phosphate cathode prepared above were cut into sizes of 2cm*4cm, respectively. In a glove box, the two electrodes were matched using a polypropylene separator from Celgard and a conventional lithium-sulfur electrolyte (composition: 1.0M LiTFSI/DME:DOL=1:1 Vol% with 2.0% LiNO 3 added, Inc.: Suzhou Duoduo Chemical Reagent Co., Ltd.), using aluminum-plastic film as a package, assembling a soft-pack battery, and obtaining a flexible lithium battery based on carbonized silk cloth with flexible lithium iron phosphate as the positive electrode material.
以上应用了具体实例对本发明进行了阐述,只是用于帮助理解本发明,并不用以限制本发明。本发明所属技术领域的技术人员依据本发明的构思,还可以做出若干简单推演、变形或替换。这些推演、变形或替换方案也落入本发明的权利要求范围内。The present invention has been described above using specific examples, which are only used to help understand the present invention, and are not intended to limit the present invention. Those skilled in the art to which the present invention pertains can also make some simple deductions, modifications or substitutions according to the concept of the present invention. These deductions, modifications or alternatives also fall within the scope of the claims of the present invention.
Claims (10)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202010548569.7A CN111740075A (en) | 2020-06-16 | 2020-06-16 | Flexible electrodes and flexible batteries based on carbonized silk fabrics |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202010548569.7A CN111740075A (en) | 2020-06-16 | 2020-06-16 | Flexible electrodes and flexible batteries based on carbonized silk fabrics |
Publications (1)
Publication Number | Publication Date |
---|---|
CN111740075A true CN111740075A (en) | 2020-10-02 |
Family
ID=72649401
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202010548569.7A Pending CN111740075A (en) | 2020-06-16 | 2020-06-16 | Flexible electrodes and flexible batteries based on carbonized silk fabrics |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN111740075A (en) |
Cited By (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN112186165A (en) * | 2020-10-10 | 2021-01-05 | 宁波大学 | Protein fiber loaded with Ni nanoparticles and preparation method and application thereof |
CN112774867A (en) * | 2021-02-22 | 2021-05-11 | 昆明理工大学 | Filtering component based on ionic liquid and micro-electric field and application |
CN112964764A (en) * | 2021-02-05 | 2021-06-15 | 深圳市刷新智能电子有限公司 | Electrode for detecting sweat marker and sweat sensor |
CN113288160A (en) * | 2021-06-02 | 2021-08-24 | 华南理工大学 | Multi-information acquisition equipment based on conductive fabric and manufacturing method |
CN113363481A (en) * | 2021-04-25 | 2021-09-07 | 广东工业大学 | Sericin crosslinked phytic acid composite binder for lithium-sulfur battery and preparation method and application thereof |
CN114188540A (en) * | 2021-12-09 | 2022-03-15 | 西安理工大学 | Preparation method and application of hypha-based carbon film conductive framework and method for preparing battery |
CN116377478A (en) * | 2023-02-10 | 2023-07-04 | 深圳市瑞麟科技有限公司 | Nano non-noble metal hydrogen evolution electrode with porous carbon carrier and preparation method thereof |
CN117403434A (en) * | 2023-09-28 | 2024-01-16 | 苏州大学 | Thermal-wet power generation material based on metal phase molybdenum disulfide double-layer conductive fabric, preparation method and application |
CN117673248A (en) * | 2023-10-26 | 2024-03-08 | 中国科学院大连化学物理研究所 | Positive electrode and preparation method and application thereof |
CN118105068A (en) * | 2024-04-30 | 2024-05-31 | 东华大学 | Method for identifying combined behavior action acting on bionic skin |
CN118919705A (en) * | 2024-10-12 | 2024-11-08 | 江苏中鲈科技发展股份有限公司 | Electrode material and preparation method thereof, electrode, battery, flexible transparent carbon fiber net and preparation method thereof, capacitor and electronic equipment |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN107634184A (en) * | 2017-09-13 | 2018-01-26 | 电子科技大学 | Flexible full solid state polymer lithium battery and preparation method thereof |
CN107994251A (en) * | 2017-12-11 | 2018-05-04 | 哈尔滨工业大学 | A kind of double charcoal cloth flexible lithium sulphur batteries and preparation method thereof |
CN109713261A (en) * | 2018-12-12 | 2019-05-03 | 浙江理工大学 | Carbonization silk fabric/transition metal oxide composite material and preparation method for flexible lithium ion battery cathode |
-
2020
- 2020-06-16 CN CN202010548569.7A patent/CN111740075A/en active Pending
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN107634184A (en) * | 2017-09-13 | 2018-01-26 | 电子科技大学 | Flexible full solid state polymer lithium battery and preparation method thereof |
CN107994251A (en) * | 2017-12-11 | 2018-05-04 | 哈尔滨工业大学 | A kind of double charcoal cloth flexible lithium sulphur batteries and preparation method thereof |
CN109713261A (en) * | 2018-12-12 | 2019-05-03 | 浙江理工大学 | Carbonization silk fabric/transition metal oxide composite material and preparation method for flexible lithium ion battery cathode |
Cited By (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN112186165A (en) * | 2020-10-10 | 2021-01-05 | 宁波大学 | Protein fiber loaded with Ni nanoparticles and preparation method and application thereof |
CN112186165B (en) * | 2020-10-10 | 2022-01-18 | 宁波大学 | Protein fiber loaded with Ni nanoparticles and preparation method and application thereof |
CN112964764A (en) * | 2021-02-05 | 2021-06-15 | 深圳市刷新智能电子有限公司 | Electrode for detecting sweat marker and sweat sensor |
CN112774867A (en) * | 2021-02-22 | 2021-05-11 | 昆明理工大学 | Filtering component based on ionic liquid and micro-electric field and application |
CN113363481A (en) * | 2021-04-25 | 2021-09-07 | 广东工业大学 | Sericin crosslinked phytic acid composite binder for lithium-sulfur battery and preparation method and application thereof |
CN113288160A (en) * | 2021-06-02 | 2021-08-24 | 华南理工大学 | Multi-information acquisition equipment based on conductive fabric and manufacturing method |
CN114188540A (en) * | 2021-12-09 | 2022-03-15 | 西安理工大学 | Preparation method and application of hypha-based carbon film conductive framework and method for preparing battery |
CN114188540B (en) * | 2021-12-09 | 2022-11-29 | 西安理工大学 | Preparation method and application of mycelium-based carbon film conductive framework and method for preparing battery |
CN116377478A (en) * | 2023-02-10 | 2023-07-04 | 深圳市瑞麟科技有限公司 | Nano non-noble metal hydrogen evolution electrode with porous carbon carrier and preparation method thereof |
CN117403434A (en) * | 2023-09-28 | 2024-01-16 | 苏州大学 | Thermal-wet power generation material based on metal phase molybdenum disulfide double-layer conductive fabric, preparation method and application |
CN117673248A (en) * | 2023-10-26 | 2024-03-08 | 中国科学院大连化学物理研究所 | Positive electrode and preparation method and application thereof |
CN117673248B (en) * | 2023-10-26 | 2025-06-20 | 中国科学院大连化学物理研究所 | A positive electrode and its preparation method and application |
CN118105068A (en) * | 2024-04-30 | 2024-05-31 | 东华大学 | Method for identifying combined behavior action acting on bionic skin |
CN118919705A (en) * | 2024-10-12 | 2024-11-08 | 江苏中鲈科技发展股份有限公司 | Electrode material and preparation method thereof, electrode, battery, flexible transparent carbon fiber net and preparation method thereof, capacitor and electronic equipment |
CN118919705B (en) * | 2024-10-12 | 2025-02-25 | 江苏中鲈科技发展股份有限公司 | Electrode material and preparation method thereof, electrode, battery, flexible transparent carbon fiber net and preparation method thereof, capacitor, electronic device |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN111740075A (en) | Flexible electrodes and flexible batteries based on carbonized silk fabrics | |
CN109713261B (en) | Carbonized silk fabric/transition metal oxide composite material for flexible lithium ion battery cathode and preparation method thereof | |
CN102983312B (en) | Preparation method of composite fiber anode material of lithium-sulfur battery | |
CN108862235B (en) | Fibrous hollow hard carbon material for sodium ion battery cathode and preparation method thereof | |
CN109103399B (en) | Functional separator for lithium-sulfur battery, preparation method thereof, and application in lithium-sulfur battery | |
CN109686953B (en) | Lithium-sulfur battery composite positive electrode material and preparation method thereof | |
CN105336930A (en) | Nitrogen-enriched carbon based/sulfur composite cathode material used for lithium sulphur batteries, and preparation method thereof | |
CN110233225B (en) | Modified diaphragm for lithium-sulfur battery and preparation method thereof | |
CN105609720B (en) | A kind of preparation method of NiPC@CNTs/S composites and application | |
CN105489901A (en) | Preparation method and application of lithium-sulfur battery three-dimensional carbon current collector | |
CN106601990A (en) | Battery positive electrode based on nitrogen-doped carbonized bacterial cellulose, lithium-sulfur battery and preparation methods therefor | |
CN111900407B (en) | A kind of lithium-sulfur battery cathode material and preparation method thereof | |
CN107732158A (en) | Lithium ion battery negative electrode preparation method, cathode pole piece and lithium ion battery | |
CN111697236A (en) | Three-dimensional current collector with multi-level structure for protecting lithium metal negative electrode and preparation method thereof | |
CN113972375B (en) | Preparation method and application of porous carbon fiber/tungsten oxide self-supporting lithium-sulfur battery positive electrode material | |
CN112670507A (en) | Preparation method of lithium-sulfur battery intermediate layer of metal selenide-loaded carbon nanofiber and lithium-sulfur battery | |
CN114388767B (en) | Nano silicon composite material, battery cathode and solid battery, and preparation methods and applications thereof | |
CN112259714A (en) | Solid-state battery composite electrode plate, preparation method thereof and solid-state battery comprising solid-state battery composite electrode plate | |
CN113506862B (en) | Nano carbon fiber composite material for lithium-sulfur battery anode and preparation method and application thereof | |
CN104752682A (en) | Preparation method of sulphur/carbon composite cathode material for lithium sulphur battery | |
CN110767901A (en) | Preserved plum-shaped iron diselenide electrode material and preparation method and application thereof | |
CN118754099A (en) | A method for preparing high-initial-efficiency nano-block sodium-ion battery negative electrode biomass hard carbon | |
CN114171730B (en) | A kind of multi-layer tubular manganese-based multi-component composite electrode material and its preparation method and application | |
CN106654182A (en) | Manganese dioxide sulfur-carbon positive electrode and preparation method | |
CN118281220B (en) | A self-supporting sodium ion battery negative electrode material and its preparation method and application |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
RJ01 | Rejection of invention patent application after publication | ||
RJ01 | Rejection of invention patent application after publication |
Application publication date: 20201002 |