CN108039523A - 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

Info

Publication number
CN108039523A
CN108039523A CN201711311996.8A CN201711311996A CN108039523A CN 108039523 A CN108039523 A CN 108039523A CN 201711311996 A CN201711311996 A CN 201711311996A CN 108039523 A CN108039523 A CN 108039523A
Authority
CN
China
Prior art keywords
battery
sponge
sample
performance
mno
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201711311996.8A
Other languages
Chinese (zh)
Other versions
CN108039523B (en
Inventor
韩金玲
吕振瑞
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Zhejiang HENGWEI battery Limited by Share Ltd
Original Assignee
韩金玲
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 韩金玲 filed Critical 韩金玲
Priority to CN201711311996.8A priority Critical patent/CN108039523B/en
Publication of CN108039523A publication Critical patent/CN108039523A/en
Application granted granted Critical
Publication of CN108039523B publication Critical patent/CN108039523B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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

Landscapes

  • 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 field, 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 modifications are carried out to it, change its surface electrical behavior, then electrostatic force is recycled, so that sponge surface coats one layer of conductive network, the sponge for being coated with conductive network to this afterwards carries out functionalization, the electrode of battery is made using the method for immersion and electro-deposition, it is tested for the property after finally being encapsulated to it, this method has of low cost, technique is simple and the characteristics of 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 field of energy storage device, and in particular to a kind of stretchable high-performance Zn-MnO2Electricity The preparing technical field in pond.
Background technology
At present, increasingly consumption, the exhaustion of traditional fossil feedstock are made with the continuous development of society and the sharp increase of population Into energy great demand between constitute serious contradiction, also, the use of fossil fuel is to environment for the survival of mankind Cause the environmental disaster such as great destruction, greenhouse effects, desertification of land, Melting Glacierss to emerge in an endless stream, although at present big Power develops all kinds of clean energy resourcies, but various clean energy resourcies, such as the utilization of wind energy, also have still there are the problem of every aspect 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 carrying out conversion makes With this just proposes the requirement of higher to the performance of battery, such as capacity.
In addition, with the continuous development of electronic technology, for example wearable smart machine in the burning hoter field of current research, it will Ask the parts for forming the smart machine are as much as possible there is flexible extensible performance, as above, this is equally to the performance of battery New requirement is proposed, this not only requires battery to have good capacity, security, it is also necessary to which battery is in certain suitable scope 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 seminars of Zhongshan University are in Chinese patent （CN106571461A）On disclose a kind of long-life, can charge and discharge Zn-MnO2Battery and its application, the Zn-MnO2 batteries Just extremely MnO2@PEDOT nano materials, anode are Zn nano materials；The MnO2@PEDOT nano materials are adopted to be first in substrate MnO is prepared with constant voltage electrodeposition process2Nanometer film, then by EDOT in-situ oxidations, in MnO2It is compound in nanometer film PEDOT obtains MnO2@PEDOT nano materials；The Zn nano materials are prepared using constant current electrodeposition process, use the party Battery prepared by method has a high-energy-density, large current density electrical characteristics, the long-life and repeats the advantage that discharge and recharge uses, but It is that the battery preparation technique prepared using this method is complicated, cost is higher, is not easy scale use.The Huilin Pan in the U.S. etc. People exists《Nature-the energy》（Nature Energy）On delivered entitled " Reversible aqueous zinc/manganese The article of oxide energy storage from conversion reactions ", in this article, Huilin Pan etc. People does the negative material of battery using α-MnO2 nanofibers, and positive electrode is done using metallic zinc, is found by research, the battery With good cycle performance, the capacity that it still can keep 92% after the circle of circulation 5000, this performance is far above current The known prior art, but this method needs first to prepare α-MnO2 nanofibers 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.
The content of the invention
Based on the above, on the premise of excellent battery performance is obtained, the present invention for solve current preparation process it is complicated, Cost is higher, and 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, first, chooses basis material of the commercial widely used sponge as electrode, will The sponge is put into after pre-treatment in prepared PDDA solution, is stirred so that untill sponge surface is covered by PDDA, Afterwards, pull soaked sponge out from PDDA solution, then the sponge is dried, obtain the finished product sponge of PDDA claddings, be denoted as Sample A；Secondly, the needs by above-mentioned sample A according to actual production, cut into suitable shape, are denoted as sample B；Again, will be upper State 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 With the mode of electro-deposition MnO is respectively coated by its surface2With Zn layers of metal, then it is packaged to processing respectively, be denoted as sample Product D and E, wherein, sample D and E are the anode and cathode of the battery.
Further, it is preferred that the PDDA solution concentrations are 0.1-0.5wt%, and the stirring is mechanical agitation, magnetic force stirs One kind in mixing or manually stirring.
Further, it is preferred that the suitable shape includes circle, rectangle, square and various set according to actual needs The shape of meter, and without concrete restriction.
Further, it is preferred that the metal nanometer line includes one kind in nano silver wire, 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, it is not necessary to Cladding pre-treatment first is carried out using PDDA, good result can also be obtained at this time.
Further, it is preferred that the metal nanometer line solution refers to solution of the concentration in 1-5mg/ml, and the graphene is molten Liquid refers to solution of the concentration in 0.1-0.5mg/ml, and the mixed proportion of the two（Volume ratio）1:Between 1-5.
Further, it is preferred that the encapsulation refers under vacuum, and processing is packaged using PDMS.
Compared with prior art, the present invention has following advantageous effects：
1st, compared with the prior art, battery preparation technique of the invention is simple, of low cost, and there is important practical application to anticipate Justice.
2nd, battery prepared by the present invention has stretchable performance, overcomes existing Zn-MnO2Battery is non-stretchable Defect, provides wearable device safe power supply important energy safeguard.
3rd, 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 ensure to stablize more than the 94% of initial capacity；In the curved of bending radius r=2mm In song test, after the circle of continuous bend 2000, it still can ensure to stablize more than the 85% of initial capacity, with fabulous Application prospect.
4th, battery prepared by the present invention does conductive material due to the use of metal nanometer line and graphene are compound, the composite material Be used in mixed way the final performance of battery had a very big impact, wherein especially the specifically effect of graphene we also need to Further research, it is not only to be used as conductive material, and by being studied using infrared detector, finding the addition of graphene has Obvious fuel factor, when metal nanometer line is used alone, we, which have surprisingly found that, does not obtain so excellent effect.Tool The mechanism of body need further to further investigate.
Brief description of the drawings
The low power scanning electron micrograph of sponge after Fig. 1 metal nanometer lines and graphene parcel；
Times scanning electron micrograph in sponge after Fig. 2 metal nanometer lines and graphene parcel；
The high power scanning electron micrograph of sponge after Fig. 3 metal nanometer lines and graphene parcel.
Embodiment
Embodiment 1
Take the sponge of business some, dried in an oven again after first it is cleaned up with deionized water, it is clean to obtain surface Sponge；Put it into the PDDA solution that prepared concentration is 0.1% and be stirred again, after stirring 10min, pull sponge out, Constantly overturn in baking oven so that PDDA is uniformly coated on sponge surface, and it is 1 by volume that the sponge coated, which is put into,:1 matches somebody with somebody The concentration of system is in the nano silver wire of 1mg/ml and the graphene mixed solution of 0.2mg/ml, after stirring 1h, pulls the sponge out simultaneously It is transferred in baking oven and constantly rotates so that nano silver wire and graphene uniform is coated on sponge surface；Finally, by above-mentioned bag The sponge covered coats one layer of MnO on its surface again using the method for conventional immersion and electro-deposition respectively2And Zn, test Bi Hou, is transferred in vacuum drying oven after obtained coating is dried and carries out PDMS infiltration encapsulation, you can obtain final products.Through Performance test is crossed, finds the sample under the rate of extension of 0.1mm/s, when deformation quantity reaches 100%, battery capacity stabilization exists The 96.5% of initial capacity；In the crooked test of bending radius r=2mm, after the circle of continuous bend 2000, battery capacity is stablized The 92% of initial capacity.
Embodiment 2
Take the sponge of business some, dried in an oven again after first it is cleaned up with deionized water, it is clean to obtain surface Sponge；It is 1 by volume that cleaned sponge, which is put into,:The copper nano-wire and 0.2mg/ml that 1 concentration prepared is 1mg/ml In graphene mixed solution, after stirring 1h, pull the sponge out and be transferred in baking oven and constantly rotate so that nano silver wire and stone Black alkene is uniformly coated on sponge surface；Finally, by the good sponge of above-mentioned cladding respectively using conventional immersion and electro-deposition Method coats one layer of MnO on its surface again2And Zn, after experiment, vacuum is transferred to after obtained coating is dried and is dried PDMS infiltration encapsulation is carried out in case, you can obtain final products.By performance test, stretching of the sample in 0.1mm/s is found Under speed, when deformation quantity reaches 100%, battery capacity stabilization in initial capacity 94.1%；In the bending of bending radius r=2mm In test, by continuous bend 2000 circle after, battery capacity stabilization in initial capacity 90%.
Embodiment 3
Take the sponge of business some, dried in an oven again after first it is cleaned up with deionized water, it is clean to obtain surface Sponge；Put it into the PDDA solution that prepared concentration is 0.5% and be stirred again, after stirring 60min, pull sponge out, Constantly overturn in baking oven so that PDDA is uniformly coated on sponge surface, and it is 1 by volume that the sponge coated, which is put into,:1 matches somebody with somebody The concentration of system is in the nano silver wire of 5mg/ml and the graphene mixed solution of 0.5mg/ml, after stirring 4h, pulls the sponge out simultaneously It is transferred in baking oven and constantly rotates so that nano silver wire and graphene uniform is coated on sponge surface；Finally, by above-mentioned bag The sponge covered coats one layer of MnO on its surface again using the method for conventional immersion and electro-deposition respectively2And Zn, test Bi Hou, is transferred in vacuum drying oven after obtained coating is dried and carries out PDMS infiltration encapsulation, you can obtain final products.Through Performance test is crossed, finds the sample under the rate of extension of 0.1mm/s, when deformation quantity reaches 100%, battery capacity stabilization exists The 95.2% of initial capacity；In the crooked test of bending radius r=2mm, after the circle of continuous bend 2000, battery capacity is stablized The 91% of initial capacity.
Comparative example 1
With embodiment 1, simply without using graphene, metal nanometer line is used alone, it has been found that obtained in other experimental procedures Sample 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；Curved In the crooked test of bilge radius r=2mm, after the circle of continuous bend 2000, battery capacity is less than the 86% of initial capacity.Need It is bright, herein, term " comprising ", "comprising" or any other variant thereof is intended to cover non-exclusive inclusion, from And process, method, article or the device for include a series of elements not only include those key elements, but also including not having The other element being expressly recited, or further include as this process, method, article or the intrinsic key element of device.
It these are only the preferred embodiment of the present invention, be not intended to limit the scope of the invention, it is every to utilize this hair The equivalent structure or equivalent flow shift that bright specification and accompanying drawing content are made, is directly or indirectly used in other relevant skills Art field, is included within the scope of the present invention.

Claims (5)

  1. A kind of 1. stretchable high-performance Zn-MnO2Battery, it is characterised in that：The battery under the rate of extension of 0.1mm/s, When deformation quantity reaches 100%, it still can ensure to stablize more than the 94% of initial capacity；Surveyed in the bending of bending radius r=2mm In examination, after the circle of continuous bend 2000, it still can ensure to stablize more than the 85% of initial capacity.
  2. A kind of 2. stretchable high-performance Zn-MnO according to claim 12The preparation method of battery, it is characterised in that：It is first First, basis material of the commercial widely used sponge as electrode is chosen, by the sponge after deionized water cleaning treatment It is put into prepared PDDA solution, is stirred so that untill sponge surface is covered by PDDA, then the sponge is dried, obtained To the finished product sponge of PDDA claddings, sample A is denoted as；Secondly, the needs by above-mentioned sample A according to actual production, it is suitable to cut into Shape, be denoted as sample B；Again, above-mentioned sample B is immersed in the mixed of prepared metal nanometer line solution and graphene in advance Close in solution, be stirred so that metal nanometer line and graphene uniform are coated on sample B surface, are denoted as sample C；Finally, The mode that obtained sample C is respectively adopted to immersion and electro-deposition is respectively coated by MnO on its surface2With Zn layers of metal, then will It is packaged processing respectively, is denoted as sample D and E, wherein, sample D and E are the anode and cathode of the battery, after assembling, i.e., It can obtain stretchable high-performance Zn-MnO2Battery.
  3. A kind of 3. stretchable high-performance Zn-MnO according to claim 22The preparation method of battery, it is characterised in that：Institute It is 0.1-0.5wt% to state PDDA solution concentrations, and the stirring is one kind in mechanical agitation, magnetic agitation or artificial stirring.
  4. A kind of 4. stretchable high-performance Zn-MnO according to claim 22The preparation method of battery, it is characterised in that：Institute The metal nanometer line stated includes the one or more in nano silver wire, 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, it is not necessary to first carry out coating preceding place using PDDA Reason.
  5. A kind of 5. stretchable high-performance Zn-MnO according to claim 22The preparation method of battery, it is characterised in that：Institute State metal nanometer line solution and refer to solution of the concentration in 1-5mg/ml, the graphene solution refers to concentration in 0.1-0.5mg/ml Solution, and the mixed proportion of the two（Volume ratio）1:Between 1-5.
CN201711311996.8A 2017-12-11 2017-12-11 A kind of stretchable high-performance Zn-MnO2The preparation method of battery Active CN108039523B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201711311996.8A CN108039523B (en) 2017-12-11 2017-12-11 A kind of stretchable high-performance Zn-MnO2The preparation method of battery

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201711311996.8A CN108039523B (en) 2017-12-11 2017-12-11 A kind of stretchable high-performance Zn-MnO2The preparation method of battery

Publications (2)

Publication Number Publication Date
CN108039523A true CN108039523A (en) 2018-05-15
CN108039523B CN108039523B (en) 2019-10-11

Family

ID=62102487

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201711311996.8A Active CN108039523B (en) 2017-12-11 2017-12-11 A kind of stretchable high-performance Zn-MnO2The preparation method of battery

Country Status (1)

Country Link
CN (1) CN108039523B (en)

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

Also Published As

Publication number Publication date
CN108039523B (en) 2019-10-11

Similar Documents

Publication Publication Date Title
Sahoo et al. Advances in pseudocapacitive and battery-like electrode materials for high performance supercapacitors
Zhang et al. Super long-life all solid-state asymmetric supercapacitor based on NiO nanosheets and α-Fe2O3 nanorods
Pan et al. Ultra-endurance flexible all-solid-state asymmetric supercapacitors based on three-dimensionally coated MnOx nanosheets on nanoporous current collectors
Pan et al. Integration: an effective strategy to develop multifunctional energy storage devices
Chen et al. Ternary oxide nanostructured materials for supercapacitors: a review
CN105869916B (en) A kind of preparation method of hydroxy cobalt oxide nanotube electrode
CN104576080B (en) An a kind of one-step electrochemistry preparation method for graphene/polyaniline flexible electrode
CN108258334A (en) A kind of composite and flexible electrode, preparation method and application
CN102509635A (en) Preparation method of flexible super capacitor based on carbon cloth
CN107256809B (en) A kind of preparation method of transparent flexible supercapacitor
CN105810455B (en) A kind of preparation method of graphene/polyaniline composite film electrode
CN103966638B (en) Preparation method for vanadium pentoxide nanowires of large-area crystalline/amorphous core-shell structures
CN103343364A (en) Method for preparing germanium nano cubic crystals through ionic liquid electro-deposition
CN105789624A (en) Array type trinickel disulfide-based composite electrode as well as preparation method and application thereof
CN108722453A (en) A kind of phosphating sludge/carbon composite nano-material for alkaline electrocatalytic hydrogen evolution
CN105932302A (en) Carbon nanotube array electrode loaded with MnO<2> nanosheets on surface, and preparation method and application therefor
CN103337381A (en) Method for fabricating flexible electrode
CN104979103B (en) A kind of spiral yarn shaped Asymmetric Supercapacitor preparation method
CN106784698A (en) Si/SiC/C composites and preparation method and lithium ion battery negative and battery
CN112421017B (en) Preparation method of binder-free water-based zinc ion battery positive electrode composite material
Anwar et al. Synthesis and electrochemical characterization of polyaniline doped cadmium oxide (PANI-CdO) nanocomposites for supercapacitor applications
CN109786135A (en) A kind of copper oxide@nickel molybdate/foam copper combination electrode material and preparation method thereof
CN108615612A (en) A kind of flower-shaped cobaltosic oxide-graphene composite material and preparation method thereof
CN107680707B (en) A kind of composition metal nano wire of core-shell structure and the preparation method and application thereof
Feng et al. High performance of electrochemically deposited NiCo2S4/CNT composites on nickel foam in flexible asymmetric supercapacitors

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
TA01 Transfer of patent application right
TA01 Transfer of patent application right

Effective date of registration: 20190912

Address after: 314000 No. 77 Zhengyang West Road, Youchegang, Xiuzhou District, Jiaxing City, Zhejiang Province

Applicant after: Zhejiang HENGWEI battery Limited by Share Ltd

Address before: 233600, No. 115-136 eddy East Road, Chengguan Town, Woyang County, Anhui, Bozhou

Applicant before: Han Jin Ling

GR01 Patent grant
GR01 Patent grant