CN105826559A - Rechargeable zinc ion battery with graphene oxide as positive electrode - Google Patents
Rechargeable zinc ion battery with graphene oxide as positive electrode Download PDFInfo
- Publication number
- CN105826559A CN105826559A CN201510002113.XA CN201510002113A CN105826559A CN 105826559 A CN105826559 A CN 105826559A CN 201510002113 A CN201510002113 A CN 201510002113A CN 105826559 A CN105826559 A CN 105826559A
- Authority
- CN
- China
- Prior art keywords
- zinc
- graphene oxide
- ion battery
- negative electrode
- positive pole
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention relates to a rechargeable zinc ion battery with graphene oxide as a positive electrode. The rechargeable zinc ion battery is composed of a positive electrode, a negative electrode, an isolating membrane between the positive electrode and the negative electrode and an electrolyte. Zinc element is mainly used as an active material of the negative electrode. An active material of the positive electrode is graphene oxide. The electrolyte is a liquid electrolyte with soluble salt of zinc and soluble salt of manganese as a solute and with water as a solvent and having ionic conductivity. The battery has characteristics of high capacity, low cost and repeated charge-discharge performance, and can be widely applied in the fields of mobile telephones, personal digital notepads, cordless telephones, electronic toys, game machines, personal audio video units, portable data terminals, palmtop computers, experimental devices and the like.
Description
Technical field
This patent belongs to field of batteries technology, is specifically related to a kind of Zinc ion battery with graphene oxide as positive pole.
Background technology
Compared to one-shot battery, secondary cell can utilize with repetitive cycling, effectively reduces the waste of resource and the pollution to environment.
Chinese patent (CN101540417A) has invented a kind of Zinc ion battery, and it is with manganese dioxide (MnO2) it is positive pole, with zinc as negative pole, with the aqueous solution containing zinc ion as electrolyte, form Rechargeable zinc ion battery.The invention of this Rechargeable zinc ion battery is based on Zn2+Two kinds of behavior: Zn of ion2+Ion has embedding and abjection behavior, still further aspect, the Zn of Rapid reversible in the manganese bioxide material in big tunnel2+Ion can be containing Zn2+The neutral electrolyte (such as zinc sulfate or zinc nitrate) of ion carries out dissolving and the deposition of Rapid reversible.This Rechargeable zinc ion battery charging and discharging capacity is probably in 200 MAH every gram (mAh/g) left and right.
For any battery, battery performance is had a great impact by the raising of electrode capacity.This patent Zinc ion battery positive pole graphene oxide replaces manganese dioxide, is electrolyte with the aqueous solution containing manganese ion and zinc ion, and the performance of battery is greatly improved, and charging and discharging capacity reaches 1200mAh/g.
Summary of the invention
Graphene oxide is the intermediate product utilizing oxidation-reduction method to prepare Graphene, is also a kind of oxide of Graphene.It is the product that graphite raw material obtains after oxidation processes, its structure is external substantial amounts of oxygen-containing functional group on the basis of Graphene: the upper layer of graphene oxide is connected to great amount of hydroxy group and epoxy radicals, in edge then with the functional group such as substantial amounts of carboxyl and carbonyl.Graphene oxide, introducing due to oxy radicals a large amount of on surface and edge, it is easy to modify and functionalization, and remain chemical stability, Graphene height conjugated structure is destroyed to a certain extent so that graphene oxide has bigger specific surface area and layer structure due to oxidizing process.
Graphene at high temperature need to expand and reduce and make with in vacuum through graphene oxide, therefore to compare Graphene preparation process simple for graphene oxide, high temperature and vacuum condition without Graphene, therefore equipment needed thereby is prepared simple, the manufacturing process of material can be significantly simplified with graphene oxide, reduce the cost of manufacture equipment and reduce the manufacturing cost of material, therefore using graphene oxide that battery manufacture cost can be greatly reduced, keep the feature of cell high-capacity simultaneously.
What the present invention proposed is a kind of Rechargeable zinc ion battery with graphene oxide as positive pole, it is made up of positive pole, negative pole, marginal isolating membrane and the neutral electrolyte containing manganese ion and zinc ion, the active substance that it is characterized in that negative pole is zinc element, positive active material is graphene oxide, electrolyte be with the soluble-salt containing zinc and manganese as solute, water is as solvent and has the liquid material of ionic conductivity.Described positive pole includes collector and the cathode film being attached on collector, and cathode film can be made up of described active material, electronic conductor and the binding agent of positive pole.Wherein, electronic conductor can use graphite, carbon black, acetylene black, Carbon fibe or carbon nanotube etc., and addition is less than the 50% of cathode film quality；Binding agent can use politef, water-soluble rubber, poly-inclined tetrafluoroethene or cellulose etc., and addition is less than the 20% of cathode film quality.Described negative pole can be moored by zinc or zinc powder is made.Negative pole can also use below scheme: negative pole includes collector and the negative electrode film being attached on collector, described negative electrode film can be made up of zinc powder and binding agent, corrosion inhibiter and/or electronic conductor can also be added further in negative electrode film, wherein, the addition of electronic conductor is less than the 50% of negative electrode film quality, the addition of corrosion inhibiter is below negative electrode film quality, and the addition of binding agent is less than the 50% of negative electrode film quality.
Present invention employs a kind of new system, utilize the redox reaction of divalent manganesetion in electrolyte that the chemical property of battery has been significantly increased.Battery is in charging process, and the divalent manganesetion generation oxidation reaction in electrolyte generates MnO2Being attached to the surface of positive pole graphene oxide, zinc ion is from MnO2Tunnel is deviate from, by ZnMn2O4Generate MnO2.In battery discharge procedure, it is attached to the MnO of positive electrode surface2Being reduced to again divalent manganesetion, the zinc ion in electrolyte is embedded in MnO2Big tunnel in generate ZnMn2O4。
Fig. 1 (a) is for be charged to the transmission electron microscope photo of graphene oxide electrode sheet during 1.55V, and during charging, surface of graphene oxide has a large amount of MnO as seen from Figure 22Generate.The transmission electron microscope photo of graphene oxide electrode sheet when Fig. 1 (b) is for discharging into 1.00V, now surface of graphene oxide does not has granule, illustrates at discharge process
In be attached to the MnO of positive electrode surface2It is reduced to again divalent manganesetion.
Graphene at high temperature need to expand and reduce and make with in vacuum through graphene oxide, therefore to compare Graphene preparation process simple for graphene oxide, high temperature and vacuum condition without Graphene, therefore equipment needed thereby is prepared simple, the manufacturing process of material can be significantly simplified with graphene oxide, reduce the cost of manufacture equipment and reduce the manufacturing cost of material, therefore using graphene oxide that battery manufacture cost can be greatly reduced, and keep the feature of cell high-capacity.
The characteristics such as the Zinc ion battery with graphene oxide as positive pole of the present invention has that capacity is high, pollution-free, low cost and good cycle.The experiment proved that, the battery capacity of this invention may be up to more than 1200mAh/g.It is contemplated that this Zinc ion battery can be widely applied to the fields such as individual digital, notepad, electronic toy, wireless phone, game machine, experimental provision, portable data terminals, palmtop computer, personal audio video-unit.
Accompanying drawing illustrates:
Legend 1:(a) Zinc ion battery with graphene oxide as positive pole is charged to 1.55V positive plate TEM；B () Zinc ion battery with graphene oxide as positive pole discharges into 1.00V positive plate TEM.
Legend 2:cell1 CV curve under speed is 0.1mV/s；
Legend 3:cell2 is in the cycle life that electric current density is during 0.1A/g；
Legend 4:cell2 provides the charging and discharging curve of 0.1A/g；
Legend 5:cell3 is in the cycle life that electric current density is during 5A/g；
Specific embodiment:
Embodiment 1:
The preparation of positive plate: be coated on stainless steel foil after 50 milligrams of graphene oxides, 14.28mg conductive agent acetylene black and 7.14mg polyfluortetraethylene of binding element are stirred, dry in 80 degrees Celsius of vacuum drying ovens, then punching obtains the positive plate 1 of a diameter of 1.5 centimetres, positive plate 2 and positive plate 3.
The preparation of negative plate: be coated in after the zinc powder of 0.35 gram, conductive agent acetylene black, CNT and binding agent are stirred on the zinc pool of 0.1 millimeters thick, it is in 80 DEG C of vacuum drying ovens to dry, then punching obtains the negative plate 1 of a diameter of 1.5cm, negative plate 2 and negative plate 3.
The preparation of electrolyte: with 2 moles of every liter of ZnSO4And 1mol/LMnSO4Aqueous solution be electrolyte.
With positive plate 1, negative plate 1 and 2mol/LZnSO4And 1mol/LMnSO4Aqueous solution do electrolyte and be assembled into battery, be designated as Cell1.After tested, Cell1 is shown in Fig. 2 at the CV curve that speed is 0.1mV/s.
By the CV curve of Fig. 2, it can be seen that there is obvious oxidoreduction peak in charge and discharge process, voltage is 1.56V, is oxidation peak during 1.61V, and represent divalent manganesetion in electrolyte is oxidized to MnO2With zinc ion from MnO2Big tunnel is deviate from.Voltage is 1.28V, is reduction peak, represents the MnO being attached to positive electrode surface during 1.37V2It is reduced to again divalent manganesetion and zinc ion is embedded into MnO2In big tunnel.
With positive plate 2, negative plate 2 and 2mol/LZnSO4And 1mol/LMnSO4Aqueous solution do electrolyte and be assembled into battery, be designated as Cell2.After tested, Cell2 is that cycle life during 0.1A/g is shown in that Fig. 3, cell2 provide the charging and discharging curve of 0.1A/g to see Fig. 4 in electric current density.
With positive plate 3, negative plate 3 and 2mol/LZnSO4And 1mol/LMnSO4Aqueous solution do electrolyte and be assembled into battery, be designated as Cell3.After tested, Cell3 is that cycle life during 5A/g is shown in Fig. 5 in electric current density.
Claims (8)
1. the Zinc ion battery with graphene oxide as positive pole, by positive pole, negative pole, marginal isolating membrane and contain zwitterion and have the electrolyte of ionic conductivity and form, it is characterised in that: the active material of described negative pole is based on zinc element；The active material of described positive pole is graphene oxide；Described electrolyte be with the soluble-salt of zinc and the soluble-salt of manganese as solute, water is as solvent and has liquid or the gel state material of ionic conductivity.
Zinc ion battery with graphene oxide as positive pole the most according to claim 1, it is characterised in that: described positive pole includes collector and the cathode film being attached on collector, and cathode film is made up of described active material, electronic conductor and the binding agent of positive pole.
Zinc ion battery with graphene oxide as positive pole the most according to claim 1, it is characterised in that: described negative pole is made up of simple metal zinc, the alloy of zinc or zinc powder.
Zinc ion battery with graphene oxide as positive pole the most according to claim 1, it is characterised in that: described negative pole includes collector and the negative electrode film being attached on collector, and this negative electrode film is made up of zinc powder and binding agent.
Zinc ion battery with graphene oxide as positive pole the most according to claim 1, it is characterised in that: described negative pole includes collector and the negative electrode film being attached on collector, and this negative electrode film is made up of zinc powder, binding agent and corrosion inhibiter.
Zinc ion battery with graphene oxide as positive pole the most according to claim 1, it is characterised in that: described negative pole includes collector and the negative electrode film being attached on collector, and this negative electrode film is made up of zinc powder, binding agent and electronic conductor.
Zinc ion battery with graphene oxide as positive pole the most according to claim 1, it is characterized in that: described negative pole includes collector and the negative electrode film being attached on collector, this negative electrode film is made up of zinc powder, binding agent, corrosion inhibiter and electronic conductor, the addition of electronic conductor is less than the 50% of negative electrode film quality, and the addition of corrosion inhibiter is less than the 1% of negative electrode film quality.
8. according to the Zinc ion battery with graphene oxide as positive pole described in any one of claim 1-7, it is characterised in that: the soluble-salt of described zinc is zinc nitrate, zinc sulfate or zinc chloride, and the soluble-salt of manganese is manganese nitrate, manganese sulfate or manganese chloride.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510002113.XA CN105826559A (en) | 2015-01-05 | 2015-01-05 | Rechargeable zinc ion battery with graphene oxide as positive electrode |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510002113.XA CN105826559A (en) | 2015-01-05 | 2015-01-05 | Rechargeable zinc ion battery with graphene oxide as positive electrode |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN105826559A true CN105826559A (en) | 2016-08-03 |
Family
ID=56513561
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510002113.XA Pending CN105826559A (en) | 2015-01-05 | 2015-01-05 | Rechargeable zinc ion battery with graphene oxide as positive electrode |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105826559A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109411833A (en) * | 2018-10-26 | 2019-03-01 | 北京大学深圳研究生院 | A kind of solid electrolyte, preparation method and application |
| CN109950500A (en) * | 2019-03-29 | 2019-06-28 | 北京航空航天大学 | A kind of manganese dioxide positive pole material for Zinc ion battery can be filled and preparation method thereof and battery |
| CN110299508A (en) * | 2019-06-24 | 2019-10-01 | 盐城市新能源化学储能与动力电源研究中心 | A kind of 3D graphite alkylene carbon anode full battery and preparation method thereof |
| CN110718719A (en) * | 2018-07-13 | 2020-01-21 | 常熟理工学院 | Rechargeable zinc ion battery |
| CN112599865A (en) * | 2020-12-10 | 2021-04-02 | 浙江浙能中科储能科技有限公司 | Neutral chargeable zinc ion battery based on large-area-capacity manganese-free positive electrode and preparation method thereof |
| CN113921797A (en) * | 2021-10-12 | 2022-01-11 | 天津工业大学 | Preparation method of graphene oxide-loaded dopamine-coated manganese dioxide nano composite structure electrode material |
-
2015
- 2015-01-05 CN CN201510002113.XA patent/CN105826559A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110718719A (en) * | 2018-07-13 | 2020-01-21 | 常熟理工学院 | Rechargeable zinc ion battery |
| CN110718719B (en) * | 2018-07-13 | 2020-10-30 | 常熟理工学院 | Rechargeable zinc ion battery |
| CN109411833A (en) * | 2018-10-26 | 2019-03-01 | 北京大学深圳研究生院 | A kind of solid electrolyte, preparation method and application |
| CN109950500A (en) * | 2019-03-29 | 2019-06-28 | 北京航空航天大学 | A kind of manganese dioxide positive pole material for Zinc ion battery can be filled and preparation method thereof and battery |
| CN110299508A (en) * | 2019-06-24 | 2019-10-01 | 盐城市新能源化学储能与动力电源研究中心 | A kind of 3D graphite alkylene carbon anode full battery and preparation method thereof |
| CN110299508B (en) * | 2019-06-24 | 2022-06-28 | 盐城师范学院 | 3D graphene based carbon positive electrode full battery and preparation method thereof |
| CN112599865A (en) * | 2020-12-10 | 2021-04-02 | 浙江浙能中科储能科技有限公司 | Neutral chargeable zinc ion battery based on large-area-capacity manganese-free positive electrode and preparation method thereof |
| CN113921797A (en) * | 2021-10-12 | 2022-01-11 | 天津工业大学 | Preparation method of graphene oxide-loaded dopamine-coated manganese dioxide nano composite structure electrode material |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US20180114987A1 (en) | Rechargeable zinc ion battery with graphene oxide as positive electrode | |
| CN102013527B (en) | Rechargeable zinc ion battery | |
| JP6143945B2 (en) | Zinc ion secondary battery and manufacturing method thereof | |
| CN204441379U (en) | Electrode for secondary battery and comprise its secondary cell and cable Type Rechargeable Battery | |
| CN105826559A (en) | Rechargeable zinc ion battery with graphene oxide as positive electrode | |
| CN106784629A (en) | A kind of lithium metal battery cathode interface method of modifying | |
| CN111785898B (en) | Cellulose-based integrated zinc ion battery and preparation method thereof | |
| CN102683757B (en) | High-capacity rechargeable zinc ion battery | |
| CN102110858B (en) | Chargeable zinc ion battery by taking oxide of vanadium as cathode | |
| CN105826520A (en) | Water system high-voltage mixed ion secondary battery based on zinc-lithium ferric manganese phosphate | |
| CN102005615B (en) | Rechargeable nickel ion battery | |
| KR20140039022A (en) | Battery | |
| CN104134818A (en) | High-energy-density lithium ion battery and preparation method thereof | |
| CN103219551A (en) | Water-system alkali metal ion power storage device | |
| CN103647104A (en) | Lithium-sulfur battery | |
| CN102097661A (en) | Rechargeable zinc ion battery using zinc manganate as anode | |
| CN109037595A (en) | Cathode of lithium protective layer and its preparation method and application | |
| Majumder et al. | Electrophoretic deposition of metal-organic framework derived porous copper oxide anode for lithium and sodium ion rechargeable cells | |
| JP5632246B2 (en) | Lithium ion secondary battery | |
| CN107799700A (en) | A kind of preparation method and applications of the barrier film of the Prussian blue modification of fabricated in situ | |
| WO2018090161A1 (en) | Rechargeable zinc ion battery employing copper metal as negative electrode current collector | |
| CN102097662B (en) | Zinc ion battery | |
| CN106711501A (en) | Novel rechargeable zinc ion battery | |
| CN103137974A (en) | Lithium ion battery anode active material, preparation method of the lithium ion battery anode active material, and lithium ion battery | |
| CN105355844A (en) | Water-injection power generation environment-friendly battery and positive electrode and battery pack thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20160803 |
|
| WD01 | Invention patent application deemed withdrawn after publication |