CN107644988A - Carbon-based lithium battery aeroge of cellulose in-situ and preparation method thereof - Google Patents
Carbon-based lithium battery aeroge of cellulose in-situ and preparation method thereof Download PDFInfo
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- CN107644988A CN107644988A CN201710851951.3A CN201710851951A CN107644988A CN 107644988 A CN107644988 A CN 107644988A CN 201710851951 A CN201710851951 A CN 201710851951A CN 107644988 A CN107644988 A CN 107644988A
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- cellulose
- aeroge
- carbon
- lithium battery
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 37
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 35
- 229920002678 cellulose Polymers 0.000 title claims abstract description 30
- 239000001913 cellulose Substances 0.000 title claims abstract description 30
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 30
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 49
- 235000010980 cellulose Nutrition 0.000 claims abstract description 29
- 238000001035 drying Methods 0.000 claims abstract description 24
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 claims abstract description 17
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 claims abstract description 17
- 239000007788 liquid Substances 0.000 claims abstract description 13
- 238000003756 stirring Methods 0.000 claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 11
- 239000002994 raw material Substances 0.000 claims abstract description 11
- 238000000498 ball milling Methods 0.000 claims abstract description 9
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 7
- 238000005406 washing Methods 0.000 claims abstract description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 12
- 239000004354 Hydroxyethyl cellulose Substances 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 claims description 6
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 6
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 6
- 238000005255 carburizing Methods 0.000 claims description 6
- 238000004132 cross linking Methods 0.000 claims description 6
- 229910052700 potassium Inorganic materials 0.000 claims description 6
- 239000011591 potassium Substances 0.000 claims description 6
- 239000012279 sodium borohydride Substances 0.000 claims description 6
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 6
- 239000001119 stannous chloride Substances 0.000 claims description 6
- 235000011150 stannous chloride Nutrition 0.000 claims description 6
- 238000002791 soaking Methods 0.000 claims description 5
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 claims description 4
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 claims description 4
- 235000014121 butter Nutrition 0.000 claims description 4
- AFOSIXZFDONLBT-UHFFFAOYSA-N divinyl sulfone Chemical compound C=CS(=O)(=O)C=C AFOSIXZFDONLBT-UHFFFAOYSA-N 0.000 claims description 4
- 239000011521 glass Substances 0.000 claims description 4
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 4
- 238000007605 air drying Methods 0.000 claims description 3
- 238000000352 supercritical drying Methods 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 claims description 2
- JDTUPLBMGDDPJS-UHFFFAOYSA-N 2-methoxy-2-phenylethanol Chemical compound COC(CO)C1=CC=CC=C1 JDTUPLBMGDDPJS-UHFFFAOYSA-N 0.000 claims description 2
- 238000004108 freeze drying Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 229940014800 succinic anhydride Drugs 0.000 claims description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 238000005516 engineering process Methods 0.000 abstract description 8
- 239000010406 cathode material Substances 0.000 abstract description 6
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- 239000000463 material Substances 0.000 description 17
- 239000003575 carbonaceous material Substances 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 238000010382 chemical cross-linking Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- QWJYDTCSUDMGSU-UHFFFAOYSA-N [Sn].[C] Chemical compound [Sn].[C] QWJYDTCSUDMGSU-UHFFFAOYSA-N 0.000 description 3
- 239000003638 chemical reducing agent Substances 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 239000002028 Biomass Substances 0.000 description 2
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 229910000906 Bronze Inorganic materials 0.000 description 1
- 239000004966 Carbon aerogel Substances 0.000 description 1
- 239000011837 N,N-methylenebisacrylamide Substances 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- MBMNDPPOHHIMDN-UHFFFAOYSA-N [Li].[C].[Sn] Chemical compound [Li].[C].[Sn] MBMNDPPOHHIMDN-UHFFFAOYSA-N 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 239000010974 bronze Substances 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 1
- 229920006037 cross link polymer Polymers 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 238000006197 hydroboration reaction Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- NNIPDXPTJYIMKW-UHFFFAOYSA-N iron tin Chemical compound [Fe].[Sn] NNIPDXPTJYIMKW-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000011859 microparticle Substances 0.000 description 1
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 1
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- -1 polyacid Chemical compound 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- RINCXYDBBGOEEQ-UHFFFAOYSA-N succinic anhydride Chemical class O=C1CCC(=O)O1 RINCXYDBBGOEEQ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
Abstract
The present invention provides a kind of carbon-based lithium battery aeroge of cellulose in-situ and preparation method thereof, comprises the following steps：(1) homogeneously scattered solution of tin system will be formed in tin source disperse water；(2) 4 10 parts by weight hydroxyethyl celluloses are added into solution of tin system, (3) addition aqueous slkali into glutinous shape liquid is stirred under normal temperature to continue to stir, add crosslinking agent to stir under normal temperature, finally polymerization forms transparent or translucent block gel at normal temperatures；(4) by the gel drying of acquisition, dried gel is carbonized again, ball milling, carrying out washing treatment obtain the carbon-based lithium battery aeroge of cellulose in-situ, aeroge excellent performance produced by the present invention, there is good gram volume in lithium cell cathode material, it ensure that it possesses preferable preparation technology and outstanding specific surface area simultaneously, preparing raw material source is wide, and preparation method is simple, it is low to prepare cost, is expected to realize industrialization large-scale production.
Description
Technical field
The present invention relates to solid state lithium battery technical field, and in particular to a kind of carbon-based lithium battery aeroge of cellulose in-situ and
Its preparation method.
Background technology
Lithium battery passes through the development of many decades, has become the most widely used energy-storage units in daily life at present,
Mainly it is used in the digital products and battery car etc. such as battery of mobile phone, Notebook Battery.As electronic product is gradually light
Quantify, miniaturization and highly integrated, requirement to battery also more and more higher.Ratio energy, shape and the security of battery are all
Significantly limit includes the development of the electronic products such as mobile phone, notebook computer and unmanned plane at present, so presently the most urgent
The problem of be to find a kind of new high specific energy electrode material, improve the energy-storage property of battery, so can just keep up with related industry
Development progress.
Novel lithium battery cathode material mainly includes grapheme material, silicon carbon material and tin carbon material, graphene at present
Material is too high due to production cost, it is difficult to realizes the industrialization production of battery material, silicon carbon material is due in charge and discharge process
Volumetric expansion is excessive to also limit its commercialization progress, and relative to first two material, tin carbon material is cheap, belongs to gold, silver and bronze
One of five big metal of iron tin, production technology is ripe, and Commercial Prospect is good.
Simple substance tin storage lithium performance is fine, but the problem of be also faced with volumetric expansion, so needing to carry out using carbon material
The processing procedure such as doping vario-property or cladding.The doping used at present is mainly ball-milling, by carbon source and tin material in ball milling
In the environment of be sufficiently mixed prepare particle diameter be micro/nano level microparticle material, improve tin carbon material performance.But due to ball milling
Overlong time, energy resource consumption are excessive, it is difficult to mass industrialized production, limit its application.Still an alternative is that template, first
Microcosmic composite construction is formed by some other materials and carbon source, dissolved other materials using some special solvents
Porous carbon source microstructure is left, then tin source filling is entered to be formed to the structure of carbon tinning, realizes the negative material of high power capacity.Phase
For a kind of above method, the performance that this method obtains is better, but preparation process is increasingly complex, the uniformity of product
It is difficult to be protected, the performance of battery is influenceed with some uncertain factors.
The performance of cell negative electrode material plays vital effect to the overall performance of battery, is formed greatly in lithium battery four
There is indispensable status in part.Existing technology is difficult to greatly mainly due to the limitation of production technology and production cost
Bulk industrial produces, and in order to make up the blank of prior art, the invention provides a kind of carbon-based lithium battery tin of cellulose in-situ
Carbon aerogels negative material loom preparation method.
The content of the invention
It is former it is an object of the invention to provide a kind of cellulose for above mentioned problem existing for current lithium cell cathode material
Carbon-based lithium battery aeroge in position and preparation method thereof, the framework material using biomass material hydroxyethyl cellulose as negative material,
Chemical cross-linking agent with epoxychloropropane etc. for aeroge, add tin source and aqueous slkali and alkaline environment be provided, in normal temperature or
The polymerisation of aeroge is completed under cryogenic conditions, forms the smooth gel rubber material of uniform outer surface, then the gel rubber material is carried out
Drying process, finally form lithium battery aeroge negative material by carbonization.
For achieving the above object, technical solution of the present invention is as follows：
A kind of preparation method of the carbon-based lithium battery aeroge of cellulose in-situ, comprises the following steps：
(1) nanometer tin, butter of tin, stannous chloride at least one are scattered in shape in 60-100 parts by weight water as tin source
Into homogeneous scattered solution of tin system；Stanniferous total amount is 2-8 parts by weight in tin source；
(2) 4-10 parts by weight hydroxyethyl celluloses are added into solution of tin system, is stirred under normal temperature, it is fully dissolved shape
Into transparent or translucent glutinous shape liquid；
(3) aqueous slkali is added into glutinous shape liquid to continue to stir, add 5-150 parts by weight of crosslinking agent under normal temperature
Stir, finally polymerization forms transparent or translucent block gel at normal temperatures；
(4) by the gel drying of acquisition, then dried gel is carbonized, ball milling, carrying out washing treatment obtain cellulose
Carbon-based lithium battery aeroge in situ.
It is preferred that in the preparation method, with reduction method for preparing nanometer tin, the raw material of nanometer tin is stannic chloride,
One or several kinds in stannous chloride or glass putty, the reducing agent used is sodium borohydride or potassium borohydride, in the raw material
Stanniferous total amount be 2-8 parts by weight, sodium borohydride or potassium borohydride are 2-15 parts by weight.
It is preferred that in the preparation method, aqueous slkali is 10-50 parts by weight of sodium hydroxide or 15- in step (3)
60 parts by weight potassium hydroxide and water are according to 1g：4ml ratio is prepared.
It is preferred that in the preparation method, the crosslinking agent in step (3) be selected from epoxychloropropane, succinic anhydride,
Succinyl chloride, divinylsulfone, polyacid, N,N methylene bis acrylamide one or more therein.
It is preferred that in the preparation method, the hydroxyethyl cellulose molecular weight is 90,000-72 ten thousand.So can be with
Ensure that crosslinked polymer forms gel.
It is preferred that in the preparation method, in step (2) hydroxyethyl cellulose and the mixing of solution of tin system stir
It is 0.5-2 hours to mix the time.It can so be well mixed.
It is preferred that in the preparation method, gel cross-linkage temperature control is in 20-50 degree, crosslinking in step (3)
Between be 3-10 hours, can be crosslinked in such time fully.
It is preferred that in the preparation method, the drying mode of gel is supercritical drying, freezing in step (4)
Dry, vacuum drying and forced air drying one kind therein, gel drying time are 0.5-4 days, and drying temperature is -50-70 degree,
Fully to dry.
It is preferred that in the preparation method, gel carburizing temperature is 800-1600 degree in step (4), during insulation
Between be 1-4 hours, can so be carbonized fully.
For achieving the above object, the present invention also provides the carbon-based lithium battery of cellulose in-situ prepared by above-mentioned preparation method
Aeroge.
The preparation method of the carbon-based lithium battery aeroge of cellulose in-situ of the present invention, with existing tin-carbon lithium battery pond negative pole technology
Compare, its protrude the characteristics of and excellent effect be：
1st, the present invention is with nature reserves biomass material hydroxyethyl cellulose raw material the abundantest, obtained this fibre
Dimension element carbon-based lithium battery aeroge excellent performance in situ, has good gram volume in lithium cell cathode material, ensures simultaneously
It possesses preferable preparation technology and outstanding specific surface area, its application development to lithium cell cathode material is had weight
The promotion meaning wanted, the short slab of the existing lithium cell cathode material of polishing.
2nd, preparing raw material source of the invention is wide, and preparation method is simple, prepares that cost is low, the raw material of use both from
Industrialized product, preparation exploitativeness is stronger, and industrialization difficulty is small, is expected to realize industrialization large-scale production.
Brief description of the drawings
Fig. 1 is that the present invention prepares cross-linked gel chemical crosslinking Principle of Process schematic diagram.
Fig. 2 is gel SEM figures after chemical crosslinking prepared by the present invention.
Embodiment
Illustrate embodiments of the present invention below by way of specific instantiation, those skilled in the art can be by this specification
Disclosed content understands other advantages and effect of the present invention easily.The present invention can also pass through specific realities different in addition
The mode of applying is embodied or practiced, the various details in this specification can also be based on different viewpoints with application, without departing from
Various modifications or alterations are carried out under the spirit of the present invention.
Fig. 2 is gel SEM figures after chemical crosslinking prepared by the present invention.Gel after being crosslinked as can be seen from Figure 2 has continuous
Uniform structure.
Embodiment 1
A kind of preparation method of the carbon-based lithium battery aeroge of cellulose in-situ, comprises the following steps：
(1) use reduction method for preparing nanometer tin, the raw material of nanometer tin be one kind in stannic chloride, stannous chloride or glass putty or
Person is several, and the reducing agent used is sodium borohydride, and stanniferous total amount is 2-8 parts by weight in the raw material, and sodium borohydride is 2 weights
Measure part.
Nanometer tin is scattered in 60 parts by weight water as tin source and forms homogeneously scattered solution of tin system；Institute is stanniferous in tin source
Total amount be 2-8 parts by weight；
(2) 4 parts by weight hydroxyethyl celluloses are added into solution of tin system, being stirred under normal temperature makes it fully molten for 0.5 hour
Solution forms transparent or translucent glutinous shape liquid；The hydroxyethyl cellulose molecular weight is 90,000-72 ten thousand.
(3) into glutinous shape liquid add aqueous slkali continue to stir, add 5 parts by weight of crosslinking agent epoxychloropropane in
Stirred under normal temperature, finally polymerization forms transparent or translucent block gel at normal temperatures；Aqueous slkali is 10 parts by weight hydrogen
Sodium oxide molybdena and water are according to 1g：4ml ratio is prepared.For gel cross-linkage temperature control at 20 degree, crosslinking time is 3 hours.
(4) by the gel drying of acquisition, drying mode is supercritical drying, and the gel drying time is 0.5 day, drying temperature
For -50 degree.Dried gel is carbonized again, carburizing temperature is 800 degree, and soaking time is 1 hour, then carries out ball
Mill, carrying out washing treatment obtain the carbon-based lithium battery aeroge of cellulose in-situ.
Embodiment 2
A kind of preparation method of the carbon-based lithium battery aeroge of cellulose in-situ, comprises the following steps：
(1) butter of tin is scattered in 100 parts by weight water as tin source and forms homogeneously scattered solution of tin system；In tin source
Stanniferous total amount be 2-8 parts by weight；
(2) 10 parts by weight hydroxyethyl celluloses are added into solution of tin system, the hydroxyethyl cellulose molecular weight is 9
Ten thousand -72 ten thousand, stir 2 hours under normal temperature, make it fully dissolve to form transparent or translucent glutinous shape liquid；
(3) add aqueous slkali into glutinous shape liquid to continue to stir, aqueous slkali is that 15 parts by weight potassium hydroxide and water are pressed
According to 1g：4ml ratio is prepared, and is added 150 parts by weight of crosslinking agent succinic anhydrides and is stirred under normal temperature, gel cross-linkage temperature
At 50 degree, crosslinking time is 10 hours for control.Finally polymerization forms transparent or translucent block gel at normal temperatures；
(4) by the gel drying of acquisition, drying mode is vacuum drying, and the gel drying time is 4 days, drying temperature 70
Degree.Dried gel is carbonized again, gel carburizing temperature be 1600 degree, soaking time be 4 hours, then ball milling, wash
Wash processing and obtain the carbon-based lithium battery aeroge of cellulose in-situ.
Embodiment 3
A kind of preparation method of the carbon-based lithium battery aeroge of cellulose in-situ, comprises the following steps：
(1) stannous chloride is scattered in 70 parts by weight water as tin source and forms homogeneously scattered solution of tin system；In tin source
Stanniferous total amount be 2-8 parts by weight；
(2) 6 parts by weight hydroxyethyl celluloses are added into solution of tin system, hydroxyethyl cellulose molecular weight is 90,000-72
Ten thousand.Stirred under normal temperature, make it fully dissolve to form transparent or translucent glutinous shape liquid；
(3) into glutinous shape liquid add aqueous slkali continue to stir 1 hour, aqueous slkali be 30 parts by weight of sodium hydroxide and
Water is according to 1g：4ml ratio is prepared.Add 50 parts by weight of crosslinking agent divinylsulfones to stir under normal temperature, gel is handed over
Join temperature control at 30 degree, crosslinking time is 5 hours, and finally polymerization forms transparent or translucent block gel at normal temperatures；
(4) by the gel drying of acquisition, drying mode is freeze-drying, and the gel drying time is 1 day, drying temperature for-
20 degree, then dried gel is carbonized, gel carburizing temperature is 1200 degree, and soaking time is 2 hours, then ball milling,
Carrying out washing treatment obtains the carbon-based lithium battery aeroge of cellulose in-situ.
Embodiment 4
A kind of preparation method of the carbon-based lithium battery aeroge of cellulose in-situ, comprises the following steps：
(1) reduction method for preparing nanometer tin is used, the raw material of nanometer tin is stannic chloride and glass putty, and the reducing agent used is hydroboration
Potassium, potassium borohydride are 15 parts by weight.
Nanometer tin, butter of tin are scattered in 80 parts by weight water as tin source and form homogeneously scattered solution of tin system；Tin
Stanniferous total amount is 2-8 parts by weight in source；
(2) 8 parts by weight hydroxyethyl celluloses are added into solution of tin system, the hydroxyethyl cellulose molecular weight is 90,000-
720000.Stirred 1.5 hours under normal temperature, make it fully dissolve to form transparent or translucent glutinous shape liquid；
(3) add aqueous slkali into glutinous shape liquid to continue to stir, aqueous slkali is that 35 parts by weight potassium hydroxide and water are pressed
According to 1g：4ml ratio is prepared.Add 120 parts by weight of crosslinking agent to stir under normal temperature, crosslinking agent includes divinyl
Sulfone, polyacid, N, N- methylene-bisacrylamides, gel cross-linkage temperature control is at 40 degree, and crosslinking time is 6 hours, so
Time can be crosslinked fully.Finally polymerization forms transparent or translucent block gel at normal temperatures；
(4) by the gel forced air drying of acquisition, drying time is 3 days, and drying temperature is 40 degree, then by dried gel
It is carbonized, gel carburizing temperature is 1400 degree, and soaking time is 3 hours, can be so carbonized fully.Then ball milling, washing
Processing obtains the carbon-based lithium battery aeroge of cellulose in-situ.
The above-described embodiments merely illustrate the principles and effects of the present invention, not for the limitation present invention.It is any ripe
Know the personage of this technology all can carry out modifications and changes under the spirit and scope without prejudice to the present invention to above-described embodiment.Cause
This, all those of ordinary skill in the art without departing from disclosed spirit with being completed under technological thought
All equivalent modifications or change, should by the present invention claim be covered.
Claims (10)
1. a kind of preparation method of the carbon-based lithium battery aeroge of cellulose in-situ, it is characterised in that comprise the following steps：
(1) nanometer tin, butter of tin, at least one be scattered in as tin source in 60-100 parts by weight water of stannous chloride are formed
Mutually scattered solution of tin system；Stanniferous total amount is 2-8 parts by weight in tin source；
(2) 4-10 parts by weight hydroxyethyl celluloses are added into solution of tin system, is stirred under normal temperature, makes it fully dissolve to be formed
Bright or translucent glutinous shape liquid；
(3) aqueous slkali is added into glutinous shape liquid to continue to stir, add 5-150 parts by weight of crosslinking agent and stirred under normal temperature
Uniformly, finally polymerization forms transparent or translucent block gel at normal temperatures；
(4) by the gel drying of acquisition, then dried gel is carbonized, ball milling, carrying out washing treatment obtain cellulose in-situ
Carbon-based lithium battery aeroge.
2. the preparation method of the carbon-based lithium battery aeroge of cellulose in-situ according to claim 1, it is characterised in that：With also
Former method prepares nanometer tin, and the raw material of nanometer tin is the one or several kinds in stannic chloride, stannous chloride or glass putty, and use is gone back
Former agent is sodium borohydride or potassium borohydride, and stanniferous total amount is 2-8 parts by weight, sodium borohydride or potassium borohydride in the raw material
For 2-15 parts by weight.
3. the preparation method of the carbon-based lithium battery aeroge of cellulose in-situ according to claim 1, it is characterised in that：Step
(3) aqueous slkali is 10-50 parts by weight of sodium hydroxide or 15-60 parts by weight potassium hydroxide and water according to 1g in：4ml ratio is matched somebody with somebody
System.
4. the preparation method of the carbon-based lithium battery aeroge of cellulose in-situ according to claim 1, it is characterised in that：Step
(3) crosslinking agent in is selected from epoxychloropropane, succinic anhydride, succinyl chloride, divinylsulfone, polyacid, N, N- di-2-ethylhexylphosphine oxides
Acrylamide one or more therein.
5. the preparation method of the carbon-based lithium battery aeroge of cellulose in-situ according to claim 1, it is characterised in that：It is described
Hydroxyethyl cellulose molecular weight is 90,000-72 ten thousand.
6. the preparation method of the carbon-based lithium battery aeroge of cellulose in-situ according to claim 1, it is characterised in that：Step
(2) hydroxyethyl cellulose and the mixing time of solution of tin system are 0.5-2 hours in.
7. the preparation method of the carbon-based lithium battery aeroge of cellulose in-situ according to claim 1, it is characterised in that：Step
(3) for gel cross-linkage temperature control in 20-50 degree, crosslinking time is 3-10 hours in.
8. the preparation method of the carbon-based lithium battery aeroge of cellulose in-situ according to claim 1, it is characterised in that：Step
(4) drying mode of gel is supercritical drying, freeze-drying, vacuum drying and forced air drying one kind therein in, gel
Drying time is 0.5-4 days, and drying temperature is -50-70 degree.
9. the preparation method of the carbon-based lithium battery aeroge of cellulose in-situ according to claim 1, it is characterised in that：Step
(4) gel carburizing temperature is 800-1600 degree in, and soaking time is 1-4 hours.
10. the carbon-based lithium battery aeroge of cellulose in-situ prepared according to preparation method described in claim 1 to 9 any one.
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