CN109713213A - A kind of metal zinc load and its preparation method and application with non-functional interface decorative layer - Google Patents
A kind of metal zinc load and its preparation method and application with non-functional interface decorative layer Download PDFInfo
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- CN109713213A CN109713213A CN201711020229.1A CN201711020229A CN109713213A CN 109713213 A CN109713213 A CN 109713213A CN 201711020229 A CN201711020229 A CN 201711020229A CN 109713213 A CN109713213 A CN 109713213A
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- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 196
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 196
- 239000011701 zinc Substances 0.000 title claims abstract description 196
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 111
- 239000002184 metal Substances 0.000 title claims abstract description 111
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 47
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 47
- 239000002134 carbon nanofiber Substances 0.000 claims abstract description 37
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 24
- 239000010439 graphite Substances 0.000 claims abstract description 24
- 239000011159 matrix material Substances 0.000 claims abstract description 19
- 229910021392 nanocarbon Inorganic materials 0.000 claims abstract description 18
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 17
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 10
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 10
- 239000004005 microsphere Substances 0.000 claims abstract description 10
- 239000011230 binding agent Substances 0.000 claims description 22
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical group CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 17
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 17
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 17
- 229910052799 carbon Inorganic materials 0.000 claims description 12
- 239000011268 mixed slurry Substances 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 9
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 claims description 8
- -1 polytetrafluoroethylene Polymers 0.000 claims description 8
- 235000007164 Oryza sativa Nutrition 0.000 claims description 6
- 239000011248 coating agent Substances 0.000 claims description 6
- 238000000576 coating method Methods 0.000 claims description 6
- 235000009566 rice Nutrition 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 238000007598 dipping method Methods 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- 238000004528 spin coating Methods 0.000 claims description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 2
- 239000010931 gold Substances 0.000 claims description 2
- 229910052737 gold Inorganic materials 0.000 claims description 2
- 240000007594 Oryza sativa Species 0.000 claims 1
- 238000004026 adhesive bonding Methods 0.000 claims 1
- 239000002105 nanoparticle Substances 0.000 claims 1
- 239000007921 spray Substances 0.000 claims 1
- 239000010410 layer Substances 0.000 description 97
- 239000002033 PVDF binder Substances 0.000 description 28
- 239000002131 composite material Substances 0.000 description 26
- 238000007766 curtain coating Methods 0.000 description 19
- 230000004048 modification Effects 0.000 description 17
- 238000012986 modification Methods 0.000 description 17
- 210000001787 dendrite Anatomy 0.000 description 16
- 229920000049 Carbon (fiber) Polymers 0.000 description 12
- 239000004917 carbon fiber Substances 0.000 description 12
- 150000001875 compounds Chemical class 0.000 description 12
- 244000137852 Petrea volubilis Species 0.000 description 10
- 210000004027 cell Anatomy 0.000 description 10
- 230000002262 irrigation Effects 0.000 description 10
- 238000003973 irrigation Methods 0.000 description 10
- 239000002002 slurry Substances 0.000 description 10
- 238000003756 stirring Methods 0.000 description 10
- 238000005498 polishing Methods 0.000 description 9
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 8
- 238000004506 ultrasonic cleaning Methods 0.000 description 7
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 description 6
- 241000209094 Oryza Species 0.000 description 5
- 238000000151 deposition Methods 0.000 description 5
- 230000008021 deposition Effects 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 5
- 238000011160 research Methods 0.000 description 5
- 239000000654 additive Substances 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 3
- 229920002873 Polyethylenimine Polymers 0.000 description 3
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 230000002401 inhibitory effect Effects 0.000 description 3
- 230000010287 polarization Effects 0.000 description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 230000008439 repair process Effects 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000010345 tape casting Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- RCEAADKTGXTDOA-UHFFFAOYSA-N OS(O)(=O)=O.CCCCCCCCCCCC[Na] Chemical compound OS(O)(=O)=O.CCCCCCCCCCCC[Na] RCEAADKTGXTDOA-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 239000002305 electric material Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical compound FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 239000003966 growth inhibitor Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002071 nanotube Substances 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- RBTVSNLYYIMMKS-UHFFFAOYSA-N tert-butyl 3-aminoazetidine-1-carboxylate;hydrochloride Chemical compound Cl.CC(C)(C)OC(=O)N1CC(N)C1 RBTVSNLYYIMMKS-UHFFFAOYSA-N 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N valeric aldehyde Natural products CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
Abstract
The present invention relates to a kind of metal zinc load and its preparation method and application with non-functional interface decorative layer, the metal zinc load includes metal Zinc Matrix and the non-functional interface decorative layer containing nano-scale carbon material for being coated on the metallic zinc matrix surface, and the nano-scale carbon material includes at least one of carbon nano-fiber, carbon nanotube, nano carbon microsphere and graphite.The present invention is used to prepare the interface-modifying layer of metal zinc load with nano-carbon material (for example, carbon nano-fiber, carbon nanotube, nano carbon microsphere, graphite etc.), and the interface-modifying layer has high-specific surface area, porous structure and excellent electric conductivity.
Description
Technical field
Present invention relates particularly to a kind of metal zinc load and preparation method thereof with non-functional interface decorative layer, belongs to zinc
Battery technology field.
Background technique
Under the overall background that energy day is becoming tight, countries in the world all are putting forth effort to study environmentally protective new energy.It is same with this
When, various electronic products are all towards the route development of miniaturization, ultra-thin membranization, require increasingly the energy density of battery
Height, traditional lithium battery is no longer satisfied human wants, therefore development high-specific energy battery becomes the following battery research
Emphasis.
Metal zinc battery with its metal zinc load have high-energy density, resourceful, cheap, equilibrium potential is low,
The features such as environmental-friendly, can carry out the excellent properties such as high current charge-discharge, have received widespread attention.But the growth of zinc dendrite
Metal zinc battery large-scale application is limited, for this problem of zinc dendrite, domestic and foreign scholars have done numerous studies.Additive
It is a kind of common zinc dendrite growth inhibitor, Stephen J (Banik S J, Akolkar R.Suppressing
dendritic growth during alkaline zinc electrodeposition using
Polyethylenimine additive [J] .Electrochimica Acta, 2015,179:475-481.) etc. in electrolyte
Middle addition polyethyleneimine (PEI) can generate inhibiting effect to zinc dendrite growth, this is because additive is adsorbed on crystal table
Face and hinder zinc ion and crystallize point discharge in zinc, and the accumulation of zinc ion concentration nearby of zinc crystallization tip accelerates zinc ion
It is shifted into deposit gap, to be conducive to deposit fractal Growth around.Sun(Sun K E K,Hoang T K A,
Doan T N L,et al.Suppression of Dendrite Formation and Corrosion on Zinc
Anode of Secondary Aqueous Batteries[J].ACS Applied Materials&Interfaces,
2017,9 (11): 9681-9687.) etc. have studied influence of the additives such as lauryl sodium sulfate to zinc dendrite, find zinc load
Pattern be effectively improved, cycle performance of battery is obviously improved.The structure for improving zinc load, prepares porous, high-ratio surface
Long-pending zinc load is also the effective way for inhibiting zinc dendrite growth.Parker(Parker J F,Chervin C N,Nelson E
S,et al. Wiring zinc in three dimensions re-writes battery performance—
dendrite-free cycling[J].Energy& Environmental Science,2014,7(3):1117-1124.)
Etc. the zinc load for reporting a kind of porous, 3D structure spongy shape, 90% can achieve to the utilization rate of zinc load, and
The growth of zinc dendrite can effectively be inhibited. Chamoun(Chamoun M,Hertzberg B J,Gupta T,et
al.Hyper-dendritic nanoporous zinc foam anodes[J].NPG Asia Materials,2015,7
) etc. (4): e178. a kind of foam zinc load is reported, Large ratio surface is conducive to the deposition of metallic zinc, and zinc preparation obtains effectively
Inhibit.By the studies above it can be concluded that improving the structure of contact of the metal zinc load with electrolyte interface, prepare porous, high
The metal zinc load of specific surface area can effectively inhibit the growth of Li dendrite, promote the cycle life of battery.
Summary of the invention
Dendrite is formed during circulating battery for metal zinc load and causes battery short circuit problem, the purpose of the present invention exists
In providing a kind of metal zinc load and its preparation method and application with non-functional interface decorative layer.
On the one hand, the present invention provides a kind of metal zinc load with non-functional interface decorative layer, the metallic zinc is negative
Pole includes metal Zinc Matrix and is coated on the non-functional interface containing nano-scale carbon material of the metallic zinc matrix surface and repairs
Layer is adornd, the nano-scale carbon material includes at least one of carbon nano-fiber, carbon nanotube, nano carbon microsphere and graphite.
The present invention is used to prepare with nano-carbon material (for example, carbon nano-fiber, carbon nanotube, nano carbon microsphere, graphite etc.)
The interface-modifying layer of metal zinc load, the interface-modifying layer have high-specific surface area, porous structure and excellent conduction
Property.Wherein (1) functional decorative layer can improve the stability of metal zinc load Yu electrolyte contacts interface, inhibit metallic zinc negative
The corrosion of pole and the functional decorative layer of dendrite effect (2) high conductivity can reduce polarization of electrode, promote the electrification of battery
Learn performance (3) high-specific surface area, porous structure functional decorative layer be conducive to the deposition of metallic zinc, can effectively inhibit zinc branch
Brilliant growth.(4) this research has the metal zinc load of non-functional interface decorative layer, preparation process letter using the tape casting preparation
It is single, it is at low cost.To sum up, there is the metal zinc load of non-functional interface decorative layer can effectively inhibit zinc branch for this research preparation
Brilliant growth, promotes the chemical property of battery, improves the cycle life of battery, and preparation process is simple, and preparation cost is cheap, tool
There is very high practical value.
Preferably, the metal Zinc Matrix is metallic zinc or kirsite.
Preferably, the diameter of the carbon nano-fiber is 1nm~10 μm, length is 100nm~100 μm；The carbon nanometer
The diameter of pipe is 1nm~1 μm, and length is 10nm~10 μm；The diameter of the nano carbon microsphere is 100nm~10 μm；The graphite
Diameter be 100nm~10 μm.
Preferably, the non-functional interface decorative layer with a thickness of 100nm~400 μm.Wherein non-functional interface decorative layer
The too thick shuttle that can hinder ion, increases the polarization of battery；The too thin requirement to technique of decorative layer is too high, and be easy to cause coating
Inhomogeneities, comprehensively consider decorative layer with a thickness of 100nm~400 μm.
Preferably, the non-functional interface decorative layer further includes binder, the binder is Kynoar, polyethylene
At least one of butyral and polytetrafluoroethylene (PTFE), 5~15wt% (bonding of Zhan Suoshu non-functional interface decorative layer gross mass
Agent content is too high to will lead to the reduction of electrode active material ratio, and the too low effect that will lead to bonding of ratio is undesirable, active material
It is easy to fall off, comprehensively considers technique and electrode performance, choose binder content and account for the non-functional interface decorative layer gross mass
5~15wt%).
On the other hand, the present invention also provides a kind of metal zinc loads with non-functional interface decorative layer as described above
Preparation method, comprising:
Solvent and nano-carbon material are mixed, mixed slurry is obtained；
Gained mixed slurry is coated in metallic zinc matrix surface, after drying, is obtained described with non-functional interface decorative layer
Metal zinc load.
Preferably, the solvent be at least one of methyl pyrrolidone, alcohol, water, the preferably described binder and
The mass ratio of solvent is (1~10): (99~90).
Preferably, the mode of the coating is spin coating, dipping, curtain coating or spraying, preferably it is cast.
Preferably, further including binder in the mixed slurry, the binder is Kynoar, polyvinyl alcohol contracting fourth
The mass ratio of at least one of aldehyde and polytetrafluoroethylene (PTFE), the nano-carbon material and binder is (95~85): (5~15).
Preferably, the temperature of the drying is 30~80 DEG C, the time is 10~20 hours.
The third aspect, the present invention also provides a kind of batteries including above-mentioned metal zinc load.
Metal zinc load prepared by the present invention be coated in surface, it is comprising nano-scale carbon material, have Gao Bibiao
The non-functional interface decorative layer of the characteristics such as area, porous structure.The non-functional interface decorative layer can be promoted metal zinc load with
The stability at electrolyte contacts interface, porous structure can effectively inhibit the growth of zinc dendrite, improve the stable circulation of battery
Property.
Detailed description of the invention
Fig. 1 is that the carbon fiber prepared in the embodiment of the present invention modifies layers composite metal zinc load structural schematic diagram；
Fig. 2 a is the zinc load assembling Symmetrical cells (zinc | zinc) for not having decorative layer, with 4mAcm-2Current density, 10
mAh·cm-2Capacity cutoff constant current charge-discharge 50 enclose after electrode shape appearance figure；
Fig. 2 b be carbon fiber in embodiment 1 modify layers composite metal zinc load assemble Symmetrical cells (zinc in embodiment 1 | it is real
Apply the zinc in example 1), with 4mAcm-2Current density, 10mAhcm-2Capacity cutoff constant current charge-discharge 50 enclose after electrode
Shape appearance figure；
Fig. 3 a is the zinc load assembling Symmetrical cells (zinc | zinc) for not having decorative layer, with 4mAcm-2Current density, 10
mAh·cm-2Capacity cutoff constant current charge-discharge voltage-time graph；
Fig. 3 b be carbon fiber in embodiment 1 modify layers composite metal zinc load assemble Symmetrical cells (zinc in embodiment 1 | it is real
Apply the zinc in example 1), with 4mAcm-2Current density, 10mAhcm-2Capacity cutoff constant current charge-discharge voltage-vs-time
Figure；
Fig. 4 is that the carbon fiber modification layers composite metal zinc load not having in the zinc load and embodiment 1 of decorative layer is with LiMn2O4
Positive assembled battery (zinc load | lithium manganate cathode) 1mAcm-2Constant current charge-discharge cycle life figure；
Fig. 5 is to prepare graphite decorative layer metal zinc load shape appearance figure in the embodiment of the present invention 2；
Fig. 6 be embodiment 2 in graphite modify layers composite metal zinc load assemble Symmetrical cells (zinc in embodiment 1 | embodiment
Zinc in 1), with 4mAcm-2Current density, 10mAhcm-2Capacity cutoff constant current charge-discharge 50 enclose after electrode pattern
Figure；
Fig. 7 is that the graphite modification layers composite metal zinc load not having in the zinc load and embodiment 2 of decorative layer is positive with LiMn2O4
Pole assembled battery (zinc load | lithium manganate cathode) 1mAcm-2Constant current charge-discharge cycle life figure；
Fig. 8 be use mass percentage concentration for 5% PVDF binder and use mass percentage concentration for 15% PVDF bond
The charge and discharge circulation life figure of agent；
Fig. 9 is layers composite metal zinc load to be modified using 100um thickness carbon fiber and using the compound gold of 500um thickness carbon fiber decorative layer
Belong to the charge and discharge circulation life figure of zinc load.
Specific embodiment
The present invention is further illustrated below by way of following embodiments, it should be appreciated that following embodiments are merely to illustrate this
Invention, is not intended to limit the present invention.
In the present invention, the metal zinc load with non-functional interface decorative layer include matrix (metal Zinc Matrix), with
And it is coated on the non-functional interface decorative layer of matrix surface formed by nano-carbon material.The metal zinc load has coating
On surface, the non-functional interface decorative layer with high-specific surface area, high conductivity and porous structure.The non-functional interface is repaired
Adoring layer is prepared by nanoscale conductive carbon material.The nanometer conductive material can be carbon nano-fiber, carbon nanotube, receive
At least one of rice carbon ball, graphite.Described matrix can be metallic zinc or kirsite.The non-functional interface decorative layer high-ratio surface
The characteristics such as long-pending and porous structure can effectively inhibit the growth of zinc dendrite, improve the cycle life of battery.The interface-modifying layer
Thickness can be 100nm~400 μm.The non-functional interface decorative layer may also include binder.The binder can be poly- inclined
At least one of vinyl fluoride, polyvinyl butyral and polytetrafluoroethylene (PTFE), can accounting for non-functional interface decorative layer gross mass, (nanometer is led
Electric material protective layer gross mass) 5~15wt%.
In the present invention, which mainly uses the tape casting to be prepared, and preparation process is simple, cost
Low, production scale is big, has very high practical value.
The pretreatment of matrix.Described matrix can be metallic zinc or kirsite.It is polished with sand paper zinc metal sheet, then will beat
Zinc metal sheet after mill carries out ultrasonic irrigation and obtains zinc metal sheet matrix.
Solvent and nano-carbon material are mixed, mixed slurry is obtained.The solvent is methyl pyrrolidone, in alcohol, water
At least one.The mass ratio of the binder and solvent can be (1~10): (99~90).It can also be wrapped in the mixed slurry
Include binder.The binder can be at least one of Kynoar, polyvinyl butyral and polytetrafluoroethylene (PTFE).It is described to receive
The mass ratio of rice carbon material and binder can be (95~85): (5~15).The nano-carbon material can be carbon nano-fiber, carbon
At least one of nanotube, nano carbon microsphere, graphite.The diameter of the carbon nano-fiber can be 1nm~10 μm, and length can be
100nm~100 μm.The diameter of the carbon nanotube can be 1nm~1 μm, and length can be 10nm~10 μm.The nano carbon microsphere
Diameter can be 100nm~10 μm.The diameter of the graphite can be 100nm~10 μm.
Mixed slurry is coated in metallic zinc matrix surface, after drying, is obtained described with non-functional interface decorative layer
Metal zinc load.The mode of the coating includes directly coating, dipping, curtain coating, spin coating or spraying etc., is preferably cast.Institute
Stating dry temperature can be 30~80 DEG C, and the time can be 10~20 hours.As an example, uniformly mixed slurry is using stream
The mode prolonged is cast matrix surface, after drying, obtains the functional boundary with characteristics such as high-specific surface area, porous structures
Face decorative layer.
The present invention measures the metallic zinc with non-functional interface decorative layer using full-automatic N2 adsorption specific surface instrument and bears
The specific surface area of functional property interface-modifying layer is 500-2000m in extremely2/g。
Enumerate embodiment further below with the present invention will be described in detail.It will similarly be understood that following embodiment is served only for this
Invention is further described, and should not be understood as limiting the scope of the invention, those skilled in the art is according to this hair
Some nonessential modifications and adaptations that bright above content is made all belong to the scope of protection of the present invention.Following examples are specific
Technological parameter etc. is also only an example in OK range, i.e. those skilled in the art can be done properly by the explanation of this paper
In the range of select, and do not really want to be defined in hereafter exemplary specific value.
Comparative example 1
By LiMn2O4 (LiMn2O4), polyvinyl butyral (PVB)+alcohol, acetylene black (8:1:1) uniform stirring slurry is made.
It is coated on steel foil and is dried, positive plate is thus made.Obtained positive plate is cut into the disk that diameter is 16mm, with
Unmodified metallic zinc is cathode, and glass fibre membrane is electrolysis as diaphragm, the solution of 1mol/L zinc sulfate+1mol/L lithium sulfate
Liquid, above-mentioned LiMn2O4 are anode assembling full battery.
Embodiment 1
It is first polished with sand paper zinc metal sheet, the zinc metal sheet after polishing is then subjected to ultrasonic irrigation.Then by Kynoar
(PVDF) it is dissolved in and prepares the PVDF binder that mass percentage concentration is 5% in methyl pyrrolidone (NMP).Then carbon is received
Rice fiber is uniformly mixed by the way of stirring with PVDF binder, remixes uniform slurry stream by the way of curtain coating
Prolong on the zinc metal sheet to after ultrasonic cleaning, then the zinc metal sheet after curtain coating is obtained into carbon nano-fiber in dry 10 hours in 70 DEG C of baking oven
Layers composite metal zinc load is modified, compound zinc load is finally cut into the cathode pole piece of required size.The carbon nano-fiber
Decorative layer with a thickness of 100 μm, specific surface area 1200m2/g.The carbon nano-fiber modification layers composite metal zinc load of preparation
Structural schematic diagram is as shown in Figure 1.The decorative layer has high-specific surface area and porous structure, and carbon fiber diameter used is 1-10
Micron, length are 20-100 microns, these carbon fibers can provide deposition site for the deposition of metallic zinc, it is possible thereby to inhibit zinc
The growth of dendrite.In order to study carbon nano-fiber decorative layer to the inhibitory effect of zinc dendrite, this research is not to have the zinc of decorative layer
Cathode and carbon fiber modification layers composite metal zinc load assemble Symmetrical cells respectively, with 4mA cm-2Current density, 10mAh
cm-2Capacity cutoff constant current charge-discharge 50 enclose after electrode pattern as shown in figures 2 a and 2b.It can be with by the comparison of bis- figure of Fig. 2 a and 2b
, it is evident that metallic zinc negative terminal surface dentrite quantity significantly reduces after being modified by carbon nano-fiber, negative terminal surface pattern is obtained
It is obviously improved.In order to test influence of the carbon nano-fiber decorative layer to battery performance, this research is not to have decorative layer
Zinc load and carbon nano-fiber modification layers composite metal zinc load assemble Symmetrical cells respectively, with 4mA cm-2Current density,
10mAh cm-2Capacity cutoff constant current charge-discharge voltage-time graph as best shown in figures 3 a and 3b.Pass through bis- figure ratio of Fig. 3 a and 3b
Relatively as can be seen that the overpotential of unmodified metal zinc load Symmetrical cells is gradually increased with the increase of cycle-index, say
The polarization of bright battery is being continuously increased.And the overpotential for the Symmetrical cells that metal zinc load assembles after carbon nano-fiber modification is passing through
Voltage platform is still very steady after crossing repeatedly circulation, illustrates that battery still keeps highly stable, it can thus be seen that carbon nanometer
Fiber-modified layer can promote the chemical property of zinc load battery.In order to test carbon nano-fiber decorative layer to the circulating battery longevity
The influence of life is respectively adopted not have the zinc load of decorative layer and carbon nano-fiber to modify layers composite metal zinc load to compare
The LiMn2O4 in electrolyte and comparative example 1 in example 1 is anode assembling full battery, with 1mA cm-2The circulation of constant current charge-discharge
Life diagram is not as shown in figure 4, it can be seen from the figure that there is the zinc load assembled battery of decorative layer to recycle battery after 127 circles
There have been the circle of circulating battery 550 left and right of short circuit, and carbon nano-fiber modification layers composite metal zinc load assembling still to keep
It is highly stable.It can be seen that carbon nano-fiber decorative layer can promote the cycle life of battery, this is because metallic zinc exists
Carbon fiber modification layer surface deposition is more uniform, and the dentrite quantity thus occurred is less, and the cycle life of battery is longer.
Embodiment 2
It is first polished with sand paper zinc metal sheet, the zinc metal sheet after polishing is then subjected to ultrasonic irrigation.Then by Kynoar
(PVDF) it is dissolved in and prepares the PVDF binder that mass percentage concentration is 5% in methyl pyrrolidone (NMP).Then by graphite
With PVDF binder using stirring by the way of uniformly mixed, remix uniform slurry using be cast by the way of be cast to it is super
Zinc metal sheet surface after sound cleaning, then by the zinc metal sheet after curtain coating dry 10 hours in 70 DEG C of baking oven to obtain graphite decorative layer compound
Compound zinc load is finally cut into the cathode pole piece of required size by metal zinc load.The graphite decorative layer with a thickness of 100
μm, specific surface area 800m2/g.The graphite of preparation modifies the structural schematic diagram of layers composite metal zinc load as shown in Fig. 5, from
It can be seen that the diameter of graphite is 1 μm~5 μm in figure, and the relatively uniform branch of graphite flake shows on the surface of zinc load
Porous form.Fig. 6 is that the graphite in embodiment 2 modifies the layers composite metal zinc load assembling Symmetrical cells (zinc in embodiment 1
| the zinc in embodiment 1), with 4mAcm-2Current density, 10mAhcm-2Capacity cutoff constant current charge-discharge 50 enclose after electricity
Pole shape appearance figure, as can be seen from the figure using the zinc load surface with graphite decorative layer, the size of dendrite obviously becomes smaller, cathode
Surface topography is obviously improved.Fig. 7 is the graphite modification layers composite metal zinc load not having in the zinc load and embodiment 2 of decorative layer
It is positive assembled battery (zinc load | lithium manganate cathode) 1mAcm with LiMn2O4-2Constant current charge-discharge cycle life figure, Cong Tuzhong
It can be seen that the cycle life of the graphite modification layers composite metal zinc load of preparation is significantly greater than not having without graphite linings and repairs
Adorn the zinc load of layer.
Embodiment 3
It is first polished with sand paper zinc metal sheet, the zinc metal sheet after polishing is then subjected to ultrasonic irrigation.Then by Kynoar
(PVDF) it is dissolved in and prepares the PVDF binder that mass percentage concentration is 5% in methyl pyrrolidone (NMP).Then carbon is received
Mitron (diameter is 100nm~1 μm, and length is 1nm~5 μm) is uniformly mixed by the way of stirring with PVDF binder,
The zinc metal sheet surface that uniform slurry is cast to after ultrasonic cleaning by the way of curtain coating is remixed, then by the zinc metal sheet after curtain coating 70
DEG C baking oven in obtain carbon nano tube modified layers composite metal zinc load within dry 10 hours, compound zinc load is finally cut into institute
Need the cathode pole piece of size.The carbon nano tube modified layer with a thickness of 100 μm, specific surface area 1800m2/g。
Embodiment 4
It is first polished with sand paper zinc metal sheet, the zinc metal sheet after polishing is then subjected to ultrasonic irrigation.Then by Kynoar
(PVDF) it is dissolved in and prepares the PVDF binder that mass percentage concentration is 5% in methyl pyrrolidone (NMP).Then by nanometer
Carbon ball (diameter is 100nm~1 μm) is uniformly mixed by the way of stirring with PVDF binder, remixes uniform slurry
Zinc metal sheet surface after being cast to ultrasonic cleaning by the way of curtain coating, then by the zinc metal sheet after curtain coating dry 10 in 70 DEG C of baking oven
Hour obtains nano carbon microsphere modification layers composite metal zinc load, and compound zinc load is finally cut into the cathode pole of required size
Piece.The nano carbon microsphere decorative layer with a thickness of 100 μm, specific surface area 1500m2/g。
Embodiment 5
It is first polished with sand paper zinc metal sheet, the zinc metal sheet after polishing is then subjected to ultrasonic irrigation.Then polyvinyl alcohol is contracted
Butyraldehyde (PVB) is dissolved in and prepares the PVB binder that mass percentage concentration is 5% in the solution of alcohol.Then by carbon Nanowire
Dimension (diameter is 1 μm~5 μm, and length is 20nm~100 μm) is uniformly mixed by the way of stirring with PVDF binder,
The zinc metal sheet surface that uniform slurry is cast to after ultrasonic cleaning by the way of curtain coating is remixed, then by the zinc metal sheet after curtain coating 70
DEG C baking oven in obtain within dry 10 hours carbon nano-fiber modification layers composite metal zinc load, finally compound zinc load is cut into
The cathode pole piece of required size.The carbon nano-fiber decorative layer decorative layer with a thickness of 100 μm, specific surface area 1200m2/
g。
Embodiment 6
It is first polished with sand paper zinc metal sheet, the zinc metal sheet after polishing is then subjected to ultrasonic irrigation.Then it incites somebody to action, polytetrafluoroethylene (PTFE)
(PTFE) it is dissolved in and prepares the PTFE binder that mass percentage concentration is 5% in the solution of water.Then by carbon nano-fiber
(diameter is 1 μm~5 μm, and length is 20nm~100 μm) is uniformly mixed by the way of stirring with PTFE binder, then is mixed
The zinc metal sheet surface that uniform slurry is cast to after ultrasonic cleaning by the way of curtain coating is closed, then by the zinc metal sheet after curtain coating at 70 DEG C
Carbon nano-fiber modification layers composite metal zinc load is obtained within dry 10 hours in baking oven, needed for being finally cut into compound zinc load
The cathode pole piece of size.The carbon nano-fiber decorative layer decorative layer with a thickness of 100 μm, specific surface area 1200m2/g。
Embodiment 7
It is first polished with sand paper zinc metal sheet, the zinc metal sheet after polishing is then subjected to ultrasonic irrigation.Then by Kynoar
(PVDF) it is dissolved in and prepares the PVDF binder that mass percentage concentration is 5% in methyl pyrrolidone (NMP).Then carbon is received
Rice fiber (diameter is 1 μm~5 μm, and length is 20nm~100 μm) is uniformly mixed by the way of stirring with PVDF binder
It closes, remixes on the zinc metal sheet after uniform slurry is cast to ultrasonic cleaning by the way of curtain coating, then the zinc metal sheet after curtain coating is existed
Carbon nano-fiber modification layers composite metal zinc load is obtained within dry 10 hours in 70 DEG C of baking oven, finally cuts compound zinc load
At the cathode pole piece of required size.The carbon nano-fiber decorative layer with a thickness of 50 μm, specific surface area 1200m2/g。
Embodiment 8
It is first polished with sand paper zinc metal sheet, the zinc metal sheet after polishing is then subjected to ultrasonic irrigation.Then by Kynoar
(PVDF) it is dissolved in and prepares the PVDF binder that mass percentage concentration is 15% in methyl pyrrolidone (NMP).Then by carbon
Nanofiber (diameter is 1 μm~5 μm, and length is 20nm~100 μm) is carried out uniformly by the way of stirring with PVDF binder
Mixing remixes uniform slurry using being cast on the zinc metal sheet after being cleaned by ultrasonic by the way of curtain coating, then by the zinc metal sheet after curtain coating
Carbon nano-fiber modification layers composite metal zinc load is obtained within dry 10 hours in 70 DEG C of baking oven, finally cuts out compound zinc load
It is cut into the cathode pole piece of required size.The carbon nano-fiber decorative layer with a thickness of 100 μm, specific surface area 1200m2/g。
As Fig. 8 be embodiment 1 use mass percentage concentration for 5% PVDF binder prepare carbon nano-fiber decorative layer and this implementation
The performance comparison figure for the carbon nano-fiber decorative layer that example uses mass percentage concentration to prepare for 15% PVDF binder.From Fig. 8
As can be seen that influence of the binder mass percentage concentration to battery performance be relatively small, use mass percentage concentration for
The later period capacity of 5% PVDF binder be slightly above use mass percentage concentration for 15% PVDF binder.
Embodiment 9
It is first polished with sand paper zinc metal sheet, the zinc metal sheet after polishing is then subjected to ultrasonic irrigation.Then by Kynoar
(PVDF) it is dissolved in and prepares the PVDF binder that mass percentage concentration is 5% in methyl pyrrolidone (NMP).Then carbon is received
Rice fiber (diameter is 1 μm~5 μm, and length is 20nm~100 μm) is uniformly mixed by the way of stirring with PVDF binder
It closes, remixes on the zinc metal sheet after uniform slurry is cast to ultrasonic cleaning by the way of curtain coating, then the zinc metal sheet after curtain coating is existed
Carbon nano-fiber modification layers composite metal zinc load is obtained within dry 10 hours in 70 DEG C of baking oven, finally cuts compound zinc load
At the cathode pole piece of required size.The carbon nano-fiber decorative layer with a thickness of 500 μm, specific surface area 1200m2/g.Fig. 9
To use 100 μ m-thick carbon nano-fibers to modify layers composite metal zinc load in embodiment 1 and being modified using 500 μ m-thick carbon fibers
The charge and discharge circulation life figure of layers composite metal zinc load.From fig. 9, it can be seen that compound using 500 μ m-thick carbon fiber decorative layers
Metal zinc load capacity early period is relatively low, needs activation time longer, and the decaying of later period battery capacity is very fast, this be mainly because
The migration of ion is hindered for decorative layer is too thick.
Claims (10)
1. a kind of metal zinc load with non-functional interface decorative layer, which is characterized in that the metal zinc load includes metal
Zinc Matrix and the non-functional interface decorative layer containing nano-scale carbon material for being coated on the metallic zinc matrix surface, it is described
Nano-scale carbon material includes at least one of carbon nano-fiber, carbon nanotube, nano carbon microsphere and graphite.
2. metal zinc load according to claim 1, which is characterized in that the metal Zinc Matrix is that metallic zinc or zinc close
Gold.
3. metal zinc load according to claim 1 or 2, which is characterized in that the diameter of the carbon nano-fiber be 1nm~
10 μm, length is 100nm~100 μm；The diameter of the carbon nanotube is 1nm~1 μm, and length is 10nm~10 μm；It is described to receive
The diameter of rice carbon ball is 100nm~10 μm；The diameter of the graphite is 100nm~10 μm.
4. metal zinc load according to any one of claim 1-3, which is characterized in that the non-functional interface decorative layer
With a thickness of 100nm~400 μm.
5. metal zinc load described in any one of -4 according to claim 1, which is characterized in that the non-functional interface decorative layer
It further include binder, the binder is at least one of Kynoar, polyvinyl butyral and polytetrafluoroethylene (PTFE), is accounted for
5~15 wt% of the non-functional interface decorative layer gross mass.
6. a kind of preparation side of the metal zinc load as described in any one of claim 1-5 with non-functional interface decorative layer
Method characterized by comprising
Solvent and nano-carbon material are mixed, mixed slurry is obtained；
Gained mixed slurry is coated in metallic zinc matrix surface, after drying, is obtained described with non-functional interface decorative layer
Metal zinc load.
7. preparation method according to claim 6, which is characterized in that the solvent is methyl pyrrolidone, in alcohol, water
At least one, the mass ratio of the preferably described binder and solvent is (1~10): (99~90).
8. preparation method according to claim 6 or 7, which is characterized in that the mode of the coating is spin coating, dipping, stream
Prolong or spray, is preferably cast.
9. preparation method a method according to any one of claims 6-8, which is characterized in that further include gluing in the mixed slurry
Agent is tied, the binder is at least one of Kynoar, polyvinyl butyral and polytetrafluoroethylene (PTFE), the nano-sized carbon
The mass ratio of material and binder is (95~85): (5~15).
10. a kind of battery including metal zinc load described in any one of claim 1-5.
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