CN108039523B - A kind of stretchable high-performance Zn-MnO2The preparation method of battery - Google Patents

A kind of stretchable high-performance Zn-MnO2The preparation method of battery Download PDF

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CN108039523B
CN108039523B CN201711311996.8A CN201711311996A CN108039523B CN 108039523 B CN108039523 B CN 108039523B CN 201711311996 A CN201711311996 A CN 201711311996A CN 108039523 B CN108039523 B CN 108039523B
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sponge
battery
sample
performance
solution
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CN108039523A (en
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韩金玲
吕振瑞
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Zhejiang HENGWEI battery Limited by Share Ltd
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Zhejiang Hengwei Battery Ltd By Share Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
    • H01M10/38—Construction or manufacture
    • 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • 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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The present invention relates to energy storage fields, and in particular to a kind of stretchable high-performance Zn-MnO2The preparation method of battery, specifically include following steps, first the sponge of business is handled, then PDDA surface coating modification is carried out to it, change its surface electrical behavior, then electrostatic force is recycled, so that sponge surface coats one layer of conductive network, functionalization is carried out to the sponge for being coated with conductive network later, use the electrode impregnated with the obtained battery of the method for electro-deposition, it is tested for the property after finally being encapsulated to it, this method has low in cost, the characteristics of simple process and excellent product performance, so that the battery is in wearable device, smart machine, the fields such as energy storage have a wide range of applications future.

Description

A kind of stretchable high-performance Zn-MnO2The preparation method of battery
Technical field
The present invention relates to a kind of manufacturing fields of energy storage device, and in particular to a kind of stretchable high-performance Zn-MnO2Electricity The preparation technical field in pond.
Background technique
Currently, the increasingly consumption of traditional fossil feedstock, exhaustion are made with the continuous development of society and the sharp increase of population At energy great demand between constitute serious contradiction, also, the use of fossil fuel is to environment for the survival of mankind Great destruction is caused, the environmental disasters such as greenhouse effects, desertification of land, Melting Glacierss emerge one after another, although at present big Power develops all kinds of clean energy resourcies, but various clean energy resourcies still have every aspect, such as the utilization of wind energy, also A big chunk wind energy is unable to direct grid-connected transmission and uses, it is also necessary to which being first stored in certain battery and then carry out conversion makes With this is just to the performance of battery, such as more stringent requirements are proposed for capacity.
In addition, with the continuous development of electronic technology, for example wearable smart machine in the burning hoter field of current research is wanted Ask the components for constituting the smart machine are as much as possible there is flexible extensible performance, as above, this is equally to the performance of battery It puts forward new requirements, this not only requires battery to have good capacity, safety, it is also necessary to which battery is in certain suitable range It is interior that there is good tensile property, preferable energy supply stability is kept while stretching, these are all current Novel electrics Pond research field urgent problem.
In this regard, scientists from all over the world conduct extensive research, if Lu Xihong seminar, Zhongshan University is in Chinese patent (CN106571461A) disclosed on a kind of long-life, can charge and discharge Zn-MnO2Battery and its application, the Zn-MnO2 battery Just extremely MnO2@PEDOT nano material, cathode are Zn nano material；The MnO2@PEDOT nano material is first to adopt in substrate MnO is prepared with constant voltage electrodeposition process2Nanometer film, then by EDOT in-situ oxidation, in MnO2It is compound in nanometer film PEDOT obtains MnO2@PEDOT nano material；The Zn nano material is prepared using constant current electrodeposition process, uses the party The advantage that the battery of method preparation is used with high-energy density, large current density electrical characteristics, long-life and repeatable charge and discharge, but It is the battery preparation technique complexity prepared using this method, higher cost is not easy scale use.The Huilin Pan in the U.S. etc. People has delivered entitled " Reversible aqueous zinc/manganese on " nature-energy " (Nature Energy) The article of oxide energy storage from conversion reactions ", in this article, Huilin Pan etc. People does the negative electrode material of battery using α-MnO2 nanofiber, does positive electrode using metallic zinc, finds after study, the battery With good cycle performance, it still can keep 92% capacity after 5000 circle of circulation, this performance is much higher than current The known prior art, but this method needs first to prepare α-MnO2 nanofiber using the method for hydro-thermal, since hydro-thermal is anti- The yield answered is extremely low, this is undoubtedly the huge obstacle for limiting the technology large-scale application.
Summary of the invention
Based on above content, under the premise of obtaining excellent battery performance, the present invention be solve current preparation process it is complicated, Higher cost, the problem of not can be mass-produced, special the following technical solutions are proposed, to obtain a kind of stretchable high-performance Zn- MnO2Battery.
Specific technical solution is as follows, firstly, commercially basis material of the widely used sponge as electrode is chosen, it will The sponge is put into prepared PDDA solution after pre-treatment, is stirred, so that until sponge surface is covered by PDDA, Later, it pulls soaked sponge out from PDDA solution, then the sponge is dried, obtain the finished product sponge of PDDA cladding, be denoted as Sample A；Secondly, above-mentioned sample A is cut into suitable shape according to the needs of actual production, it is denoted as sample B；It again, will be upper It states sample B to be immersed in the mixed solution of prepared metal nanometer line solution and graphene in advance, be stirred, so that metal Nano wire and graphene uniform are coated on sample B surface, are denoted as sample C；Finally, immersion is respectively adopted in obtained sample C MnO is respectively coated by its surface with the mode of electro-deposition2With Zn layers of metal, then it is packaged respectively to processing, be denoted as sample Product D and E, wherein sample D and E are the cathode and anode of the battery.
Further, it is preferred that the PDDA solution concentration is 0.1-0.5wt%, and the stirring is mechanical stirring, magnetic force stirs One of mix or manually stir.
Further, it is preferred that the suitable shape includes circle, rectangle, square and various sets according to actual needs The shape of meter, and without concrete restriction.
Further, it is preferred that the metal nanometer line includes one of silver nanowires, copper nano-wire, nanowires of gold Or it is several, and when using copper nano-wire, directly the sponge handled well can be put into copper nano-wire and be stirred, do not needed Cladding pre-treatment first is carried out using PDDA, at this time also available good result.
Further, it is preferred that the metal nanometer line solution refers to concentration in the solution of 1-5mg/ml, and the graphene is molten Liquid refers to concentration in the solution of 0.1-0.5mg/ml, and the mixed proportion (volume ratio) of the two is between 1:1-5.
Further, it is preferred that the encapsulation refers under vacuum conditions, is packaged processing using PDMS.
Compared with prior art, the present invention has advantageous effects below:
1, compared with the prior art, battery preparation technique of the invention is simple, low in cost, has important practical application Meaning.
2, battery prepared by the present invention has stretchable performance, overcomes existing Zn-MnO2Battery is non-stretchable Defect provides important energy safeguard to wearable device safe power supply.
3, battery prepared by the present invention has good tensile property, by experimental test, in the rate of extension of 0.1mm/s Under, when deformation quantity reaches 100%, still can guarantee to stablize 94% or more of initial capacity；In the curved of bending radius r=2mm In song test, after the circle of continuous bend 2000, it still can guarantee to stablize 85% or more of initial capacity, have fabulous Application prospect.
4, battery prepared by the present invention is due to using metal nanometer line and graphene is compound does conductive material, the composite material Be used in mixed way the final performance of battery had a very big impact, wherein the specifically effect of especially graphene we also need Further research is not only to be used as conductive material, by being studied using infrared detector, it is found that the addition of graphene has Apparent fuel factor, when metal nanometer line is used alone, we have surprisingly found that there is no obtain so excellent effect.Tool The mechanism of body need further to further investigate.
Detailed description of the invention
The low power scanning electron micrograph of sponge after Fig. 1 metal nanometer line and graphene package；
Times scanning electron micrograph in sponge after Fig. 2 metal nanometer line and graphene package；
The high power scanning electron micrograph of sponge after Fig. 3 metal nanometer line and graphene package.
Specific embodiment
Embodiment 1
It takes the sponge of business several, is dried in an oven again after first cleaning up it with deionized water, it is dry to obtain surface Net sponge；It puts it into the PDDA solution that prepared concentration is 0.1% and is stirred again, after stirring 10min, pull sea out The sponge coated is put into and is by volume so that PDDA is uniformly coated on sponge surface by silk floss, in an oven constantly overturning The concentration that 1:1 is prepared is after stirring 1h, to pull the sea out in the silver nanowires of 1mg/ml and the graphene mixed solution of 0.2mg/ml It is continuous and be transferred in baking oven and constantly rotate, so that silver nanowires and graphene uniform are coated on sponge surface；Finally, by upper It states the sponge coated and coats one layer of MnO again on its surface using the method for conventional immersion and electro-deposition respectively2And Zn, it is real After testing, PDMS infiltration encapsulation is carried out by being transferred in vacuum drying oven after the drying of obtained coating, final production can be obtained Product.By performance test, the sample is found under the rate of extension of 0.1mm/s, when deformation quantity reaches 100%, battery capacity is steady It is scheduled on the 96.5% of initial capacity；In the crooked test of bending radius r=2mm, after the circle of continuous bend 2000, battery capacity Stablize the 92% of initial capacity.
Embodiment 2
It takes the sponge of business several, is dried in an oven again after first cleaning up it with deionized water, it is dry to obtain surface Net sponge；Cleaned sponge is put into be by volume 1:1 prepare concentration be 1mg/ml copper nano-wire and 0.2mg/ In the graphene mixed solution of ml, after stirring 1h, pulls the sponge out and be transferred in baking oven and constantly rotate, so that silver nanowires Sponge surface is coated on graphene uniform；Finally, the good sponge of above-mentioned cladding is sunk using conventional immersion and electricity respectively Long-pending method coats one layer of MnO on its surface again2And Zn, it is true by being transferred to after the drying of obtained coating after experiment PDMS infiltration encapsulation is carried out in empty baking oven, and final products can be obtained.By performance test, find the sample 0.1mm/s's Under rate of extension, when deformation quantity reaches 100%, battery capacity is stablized the 94.1% of initial capacity；Bending radius r=2mm's In crooked test, after the circle of continuous bend 2000, battery capacity is stablized the 90% of initial capacity.
Embodiment 3
It takes the sponge of business several, is dried in an oven again after first cleaning up it with deionized water, it is dry to obtain surface Net sponge；It puts it into the PDDA solution that prepared concentration is 0.5% and is stirred again, after stirring 60min, pull sea out The sponge coated is put into and is by volume so that PDDA is uniformly coated on sponge surface by silk floss, in an oven constantly overturning The concentration that 1:1 is prepared is after stirring 4h, to pull the sea out in the silver nanowires of 5mg/ml and the graphene mixed solution of 0.5mg/ml It is continuous and be transferred in baking oven and constantly rotate, so that silver nanowires and graphene uniform are coated on sponge surface；Finally, by upper It states the sponge coated and coats one layer of MnO again on its surface using the method for conventional immersion and electro-deposition respectively2And Zn, it is real After testing, PDMS infiltration encapsulation is carried out by being transferred in vacuum drying oven after the drying of obtained coating, final production can be obtained Product.By performance test, the sample is found under the rate of extension of 0.1mm/s, when deformation quantity reaches 100%, battery capacity is steady It is scheduled on the 95.2% of initial capacity；In the crooked test of bending radius r=2mm, after the circle of continuous bend 2000, battery capacity Stablize the 91% of initial capacity.
Comparative example 1
Other experimental procedures do not use graphene only with embodiment 1, and metal nanometer line is used alone, it has been found that system The sample obtained is under the rate of extension of 0.1mm/s, and when deformation quantity reaches 100%, battery capacity is less than the 87.9% of initial capacity； In the crooked test of bending radius r=2mm, after the circle of continuous bend 2000, battery capacity is less than the 86% of initial capacity.It needs It is noted that herein, the terms "include", "comprise" or its any other variant are intended to the packet of nonexcludability Contain, so that the process, method, article or the device that include a series of elements not only include those elements, but also including Other elements that are not explicitly listed, or further include for this process, method, article or the intrinsic element of device.
The above is only a preferred embodiment of the present invention, is not intended to limit the scope of the invention, all to utilize this hair Equivalent structure or equivalent flow shift made by bright specification and accompanying drawing content is applied directly or indirectly in other relevant skills Art field, is included within the scope of the present invention.

Claims (4)

1. a kind of preparation method of stretchable high-performance Zn-MnO2 battery, it is characterised in that: the following steps are included: firstly, choosing Commercial basis material of the widely used sponge as electrode is taken, which is put into after deionized water cleaning treatment and is matched It in the PDDA solution made, is stirred, so that until sponge surface is covered by PDDA, then the sponge is dried, obtain PDDA The finished product sponge of cladding, is denoted as sample A；Secondly, above-mentioned sample A is cut into suitable shape according to the needs of actual production, It is denoted as sample B；Again, above-mentioned sample B is immersed in the mixed solution of prepared metal nanometer line solution and graphene in advance In, it is stirred, so that metal nanometer line and graphene uniform are coated on sample B surface, is denoted as sample C；Finally, will obtain Sample C immersion is respectively adopted and the mode of electro-deposition is respectively coated by MnO2 and Zn layers of metal on its surface, then distinguished It is packaged processing, is denoted as sample D and E, wherein sample D and E are the cathode and anode of the battery, after assembling, be can be obtained Stretchable high-performance Zn-MnO2 battery；
The battery is under the rate of extension of 0.1mm/s, when deformation quantity reaches 100%, still can guarantee to stablize in initial capacity 94% or more；In the crooked test of bending radius r=2mm, after the circle of continuous bend 2000, it still can guarantee to stablize 85% or more of initial capacity.
2. a kind of preparation method of stretchable high-performance Zn-MnO2 battery according to claim 1, it is characterised in that: The PDDA solution concentration is 0.1-0.5wt%, and the stirring is one of mechanical stirring, magnetic agitation or artificial stirring.
3. a kind of preparation method of stretchable high-performance Zn-MnO2 battery according to claim 1, it is characterised in that: The metal nanometer line includes one or more of silver nanowires, copper nano-wire, nanowires of gold, and works as and use copper nano-wire When, directly the sponge handled well can be put into copper nano-wire and be stirred, do not need first to carry out coating preceding place using PDDA Reason.
4. a kind of preparation method of stretchable high-performance Zn-MnO2 battery according to claim 1, it is characterised in that: The metal nanometer line solution refers to concentration in the solution of 1-5mg/ml, and the graphene solution refers to concentration in 0.1-0.5mg/ The solution of ml, and the mixed proportion (volume ratio) of the two is between 1:1-5.
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Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105989911A (en) * 2015-02-10 2016-10-05 北京大学 Graphene and metal nanowire composite transparent and conductive plastic film, manufacturing method and application thereof

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105989911A (en) * 2015-02-10 2016-10-05 北京大学 Graphene and metal nanowire composite transparent and conductive plastic film, manufacturing method and application thereof

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