CN110518295A - One kind can fill zinc-base battery - Google Patents
One kind can fill zinc-base battery Download PDFInfo
- Publication number
- CN110518295A CN110518295A CN201910792425.3A CN201910792425A CN110518295A CN 110518295 A CN110518295 A CN 110518295A CN 201910792425 A CN201910792425 A CN 201910792425A CN 110518295 A CN110518295 A CN 110518295A
- Authority
- CN
- China
- Prior art keywords
- zinc
- electrolyte
- graphite
- base battery
- battery
- 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
-
- 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
- H01M10/24—Alkaline accumulators
- H01M10/26—Selection of materials as electrolytes
-
- 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
- H01M10/24—Alkaline accumulators
- H01M10/28—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
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- 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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0002—Aqueous electrolytes
- H01M2300/0014—Alkaline electrolytes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0088—Composites
- H01M2300/0091—Composites in the form of mixtures
-
- 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)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The present invention provides one kind can fill zinc-base battery comprising graphite anode, zinc load and electrolyte, the active material in the graphite anode is graphite, and the electrolyte includes soluble zinc salt and organic solvent.Battery made by the present invention is in charge and discharge process, anion in the electrolyte quick intercalation/deintercalation in positive graphite linings, the compatibility of the deposition/precipitation reversible in zinc load of simultaneous zinc ion, electrolyte and graphite anode and zinc load is good, and Zn deposits/be precipitated coulombic efficiency height.The zinc-base battery can realize complete charge and discharge in the short time, and energy/power density is high, have excellent long circulating stability.
Description
Technical field
The present invention relates to a kind of batteries, and zinc-base battery can be filled by concretely relating to one kind.
Background technique
Lithium ion battery energy/power density height, long service life, have been achieved with huge in portable
Success, and gradually develop to fields such as new-energy automobile, smart grids.However, lithium resource is short, safety is low, price is high etc.
Factor limits it in the application of extensive energy storage field.Metallic zinc has high abundance, low cost, high safety, low combustible, nothing
The features such as toxicity, high chemical stability, can be directly used as negative electrode material and be applied to fill in zinc-base battery (RZBs) system, and its
Theoretical capacity is up to 820 mAh/g.Therefore, can fill zinc-base battery is considered as an ideal choosing in extensive energy storage field
It selects, in recent years by the extensive concern of researcher.
In conventional alkaline electrolyte, zinc metal negative electrode be faced with Zn deposit/be precipitated low coulombic efficiency, dendritic growth and
By-product (such as ZnO or Zn (OH)2) generate etc. main problems, reduce the Disposal degree of battery.The neutrality or weak acid of recent report
Property aqueous electrolyte can inhibit zinc dendrite growth to a certain extent, but zinc deposition/precipitation coulombic efficiency still needs to be mentioned
It rises.In addition, the electrochemical window of aqueous electrolyte is relatively narrow (~ 1.23 V), overcharge or over-discharge in the case of there is analysis oxygen or liberation of hydrogen row
For this will affect the energy density and service life of water system zinc-base battery.
In terms of positive electrode, anode average discharge volt reported at present is lower, such as V2O5(~ 0.85 V), MnO2
(~ 1.35 V), KCuFe (CN)6(~ 1.65 V), Na3V3(PO4)3(1.1 V) and ZnNi0.5Mn0.5CoO4(~ 1.75 V) etc., this
Limit the energy density of battery entirety；Simultaneously as there are dissolution phenomenas in aqueous electrolyte for oxide anode material, lead
The cyclical stability for sending a telegraph pond is poor；In addition, the Zn of high quality and high-valence state2+Ion desolvation energy barrier is big, and electrode reaction is dynamic
Mechanics is low, this can reduce the high rate performance of battery.
In conclusion that how to develop with high voltage, high rate capability and long circulation life novel fills zinc-base battery
It is one of current problem to be solved.
Summary of the invention
An object of the present invention is to provide a kind of for that can fill the electrolyte of zinc-base battery.
The second object of the present invention is to provide one kind to fill zinc-base battery.
The third object of the present invention is to provide a kind of preparation method that can fill zinc-base battery.
An object of the present invention is achieved in that
It is a kind of for the electrolyte of zinc-base battery can be filled, the electrolyte includes soluble zinc salt and organic solvent；It is described solvable
Property zinc salt include double trifluoromethanesulfonimide zinc (Zn (TFSI)2) or hexafluorophosphoric acid zinc Zn (PF6)2, and the soluble zinc salt
Concentration be 0.2 ~ 2.5 mol/L；The organic solvent is in acetonitrile, propene carbonate, trimethyl phosphate and triethyl phosphate
Any one or a few.
Preferably, the concentration of the soluble zinc salt is 0.5 ~ 2 mol/L.
Preferably, the organic solvent is acetonitrile (AN).
The electrolyte can be used following methods and be made: in high-purity argon gas environment, by the soluble Zn of specific quantity
Salt electrolyte salt is dissolved in organic solvent, makes 0.2 ~ 2.5 mol/L of concentration of the soluble zinc salt, preferably 0.5 ~ 2 mol/L,
It is uniformly mixed, is completely dissolved the soluble zinc salt electrolytic salt to obtain the final product.
The second object of the present invention is to what is be achieved:
One kind can fill zinc-base battery, including anode, cathode and electrolyte, and described just extremely graphite anode, the cathode are negative for zinc
Pole, the electrolyte are the electrolyte for being previously used for fill zinc-base battery.
The graphite anode includes lamellar graphite, and anion intercalation/deintercalation may be implemented in high voltage.
Layered graphite includes that layered conductive graphite and/or flakey electrically conductive graphite specifically can be conductive for commercialization
Any one or a few in graphite (KS4, KS6 type etc.) or crystalline flake graphite (SFG6L, SFG75 type etc.), can also using it is a variety of not
The mixture of same type graphite.
Optionally, the graphite anode includes positive electrode active materials graphite, binder and collector, is by graphite and to glue
Knot agent be mixed and made into slurry after be evenly applied on collector and after drying made from.The binder is carboxymethyl cellulose
Sodium (CMC) or polyvinylidene fluoride (PVDF)；Preferably, the mass ratio of the graphite and the binder is 9: 1 ~ 8: 2；It will
Graphite and binder are scattered in water or organic solvent, and preferred organic solvent is N, N- dimethyl pyrrolidone (NMP)；Institute
Stating collector is titanium foil or stainless steel foil, and thickness is preferably 10 ~ 30 μm.
Specifically, graphite and binder 9:1 in mass ratio are mixed, is scattered in water or N, N- dimethyl pyrrolidone
(NMP) slurry is made in, is evenly applied on titanium foil or stainless steel foil with a thickness of 10 ~ 30 μm, 100 DEG C obtained by drying described
Anode.
The zinc load is made of metallic zinc foil or spherical zinc powder；The metallic zinc foil with a thickness of 10 ~ 30 μm,
The granularity of the spherical shape zinc powder is 100 nm ~ 1 μm.
The zinc load is made of metallic zinc foil, is that metallic zinc foil is cut to specific dimensions.
When the zinc load is made of spherical zinc powder, preparation method includes: to gather spherical zinc powder with aqueous binder
Ethylene oxide is uniformly mixed according to 98: 2 weight ratio, obtains mixture；The water for accounting for mixture weight 3% is added into mixture,
It is ground into slurry, is coated on a thickness of on 10 ~ 30 μm of stainless steel foil, for coat with a thickness of 20 ~ 50 μm, 100 DEG C of vacuum are dry
Dry 12 hours.
The soluble zinc salt includes double trifluoromethanesulfonimide zinc (Zn (TFSI)2) or hexafluorophosphoric acid zinc Zn (PF6)2,
The concentration of the soluble zinc salt is 0.2 ~ 2.5 mol/L, preferably 0.5 ~ 2 mol/L.
The organic solvent is acetonitrile (AN), propene carbonate (PC), trimethyl phosphate (TMP) and triethyl phosphate
(TEP) any one or a few in, preferably acetonitrile (AN).
The electrolyte can be used following methods and be made: in high-purity argon gas environment, by the soluble Zn of specific quantity
Salt electrolyte salt is dissolved in organic solvent, makes 0.2 ~ 2.5 mol/L of concentration of the soluble zinc salt, preferably 0.5 ~ 2 mol/L,
It is uniformly mixed, is completely dissolved the soluble zinc salt electrolytic salt to obtain the final product.
The third object of the present invention is achieved in that
A kind of preparation method for filling zinc-base battery, in high-purity argon gas environment, according to negative electrode casing, zinc load, diaphragm, electrolysis
Liquid, graphite anode, gasket, elastic slice, anode cover sequence successively stack, to anode and cathode between diaphragm on aforementioned electrolysis is added dropwise
Liquid makes its complete wetting, encapsulate battery to get.
The diaphragm is glass fibre membrane or polyethylene nonwoven.
The present invention uses graphite anode, metal zinc load and organic electrolyte to construct, and one kind is novel to fill zinc-base cell body
System.The oxidation/reduction stability of electrolyte is high, ionic conductivity is excellent, and viscosity is low, and coulombic efficiency height is precipitated in Zn deposition, and
It is good with the compatibility of graphite anode and zinc load.TFSI in electrolyte-Or PF6 -Anion can be in positive graphite linings
Quick intercalation/deintercalation, the deposition/precipitation reversible in cathode of simultaneous zinc ion, and zinc load surface is formed without dendrite.It should
Zinc-graphite cell can realize fully charged or electric discharge in a short time, and average discharge volt is higher than existing zinc-base battery system, energy
Amount/power density height, good cycling stability.
Detailed description of the invention
Fig. 1 is that the present invention can fill zinc-base battery operation principle schematic diagram.
Fig. 2 is 1 mol/L Zn (TFSI) prepared by embodiment 12The voltage window test CV figure of-AN electrolyte.
Fig. 3 is 1 mol/L Zn (TFSI) prepared by embodiment 12- AN electrolyte stable circulation in Zn/Zn Symmetrical cells
Property test chart.
Fig. 4 is scanning electron microscope (SEM) figure of the anode of original graphite used in embodiment 1.
Fig. 5 is the preparation of embodiment 1 based on 1 mol/L Zn (TFSI)2The charge and discharge for filling zinc-base battery of-AN electrolyte
Electric curve.
Fig. 6 is the preparation of embodiment 1 based on 1 mol/L Zn (TFSI)2The circulation for filling zinc-base battery of-AN electrolyte
Performance map.
Fig. 7 is the preparation of embodiment 1 based on 1 mol/L Zn (TFSI)2The multiplying power for filling zinc-base battery of-AN electrolyte
Performance map.
Specific embodiment
Below with reference to embodiment, the present invention is further elaborated, and following embodiments are only as explanation, not with any
Mode limits the scope of the invention.
The process and method being not described in detail in the following embodiments are conventional method well known in the art, institute in embodiment
It is to analyze pure or LITHIUM BATTERY with reagent, and it is commercially available or pass through method well known within the skill of those ordinarily skilled and prepare.Under
Stating embodiment realizes the purpose of the present invention.
In following embodiments, can fill zinc-base battery main functional parts includes anode, cathode and electrolyte, wherein uses stone
Black positive plate makees cathode as anode, metallic zinc foil (zinc powder), uses glass fibre membrane as diaphragm between positive and negative anodes, and is added dropwise each
The organic electrolyte of embodiment preparation.
Graphite positive plate is prepared in the following way: by KS6 type graphite and sodium carboxymethylcellulose (CMC) binder by matter
Amount is mixed than 9:1, is dispersed in water, and grinds 1 hour, slurry is made, is evenly applied to titanium foil or stainless steel with a thickness of 20 μm
On foil, 100 DEG C of drying are made graphite positive plate (attached drawing 4).
When cathode is made using metallic zinc foil, the metallic zinc foil with a thickness of 20 μm is cut to the circle that diameter is 12 mm
Piece is directly used as negative electrode tab.
The method for using spherical zinc powder to prepare cathode includes: to glue granularity with aqueous for the spherical zinc powder of 100 nm ~ 1 μm
Knot agent polyethylene glycol oxide is uniformly mixed according to the weight ratio of 98:2, obtains mixture；It is added into mixture and accounts for mixture weight
3% water, is ground into slurry, and coated on the stainless steel foil with a thickness of 20 μm, coat is with a thickness of true at 20 ~ 50 μm, 100 DEG C
Sky is 12 hours dry, and negative electrode tab can be obtained.
Embodiment 1
Configure electrolyte: in high-purity argon gas environment, by 0.625 g Zn (TFSI)2It is dissolved in 1 mL AN, fullys shake, make
Zinc salt is completely dissolved, and is configured to 1 mol/L Zn (TFSI)2- AN electrolyte.
Battery assembly: in high-purity argon gas environment, make anode, 1 mol/ of above-mentioned configuration with the graphite positive plate prepared
L Zn(TFSI)2- AN solution makees electrolyte, and the metallic zinc foil cut makees cathode, makees with a thickness of the glass fibre membrane of 0.2 mm
It for diaphragm, successively stacks, organizes stacked according to the sequence of negative electrode casing, cathode, diaphragm, electrolyte, anode, gasket, elastic slice, anode cover
Layer structure, 80 μ L electrolyte manufactured in the present embodiment are added dropwise on diaphragm between a positive electrode and a negative electrode infiltrates diaphragm, compacting envelope
Dress, zinc-base battery can be filled by being made.The working principle that gained can fill zinc-base battery is as shown in Figure 1.
Following performance tests are carried out to gained electrolyte, battery:
(1) electrolyte voltage window
The voltage window of electrolyte passes through Zn/Ti battery testing.In high-purity argon gas glove box, use titanium foil (Ti) as work electricity
Pole, for zinc foil (Zn) as to electrode and reference electrode, glass fibre is used as diaphragm, and 80 μ L the present embodiment are added dropwise and prepare electrolyte,
Standard CR2032 type button cell is made.Battery is tested using Cyclic voltammetric method (CV), scanning speed is set as 1
MV/s, test voltage section are -0.25 ~ 3 V.Data are recorded with CHI660E type electrochemical workstation.
Acquired results are as shown in Figure 2, the results showed that, 1 mol/L Zn (TFSI) of electrolyte manufactured in the present embodiment2- AN exists
Low potential shows stable zinc deposition/precipitation, and the partially stabilized voltage window of high potential is up to 2.8 V(vs. Zn2+/ Zn).
(2) conductivity
The conductivity that the present embodiment prepares electrolyte is tested with AC impedence method, experimental data is in CHI660E type electrochemical operation
It stands record.The result shows that it is 28mS/cm that the present embodiment, which prepares electrolytic conductivity,.
(3) viscosity
Measuring the present embodiment at room temperature to prepare the viscosity of electrolyte with MDJ-5S type viscosity apparatus is 0.4 mPa/s.
(4) stability of the electrolyte to zinc load
The test of Zn/Zn Symmetrical cells cyclical stability: in high-purity argon gas glove box, working electrode and zinc is used to electrode
Foil.Make diaphragm with glass fibre between two zinc foils, 80 μ L electrolyte be added dropwise, are assembled into Zn/Zn Symmetrical cells, test its it is long when
Between in cyclic process electrolyte stability.It is tested with the blue electric battery test system of CT2001A type, in 0.5 mA/cm2's
Cycle charge-discharge under current density, in each cycle, first constant-current discharge 30 minutes, rear constant-current charge 30 minutes.
Acquired results are as shown in figure 3, it can be seen from the figure that symmetrical in Zn/Zn using electrolyte made from the present embodiment
It is more than hour that circulation 200 can be stablized in battery.
(5) novel to fill zinc-base circulating battery stability
The novel zinc-base battery that fills that the present embodiment is assembled is in 1 ~ 2.55 V(vs. Zn2+/ Zn) voltage range in carry out
Charge-discharge test, current density 1.0A/g.
The charging and discharging curve of prepared zinc-base battery is to report at present as shown in figure 5, average discharge volt is 2.2 V
The peak filled in zinc-base battery；Cycle performance figure is as shown in fig. 6, it can be seen from the figure that battery is in 1.0 A/g electric currents
The reversible capacity of 43 mAh/g can be achieved under density；After circulation 2000 times, capacity retention ratio is up to 94%, shows fabulous length
Cyclical stability.
(6) the novel high rate performance for filling zinc-base battery
Under different current densities, high rate performance test is carried out to the zinc-base battery assembled, voltage range is 1 ~ 2.55 V
(vs. Zn2+/ Zn), current density is respectively 0.1,0.2,0.5,1.0,1.5,2.0,3.0 and 4.0 A/g.
The novel zinc-base battery that fills of the present embodiment assembly shows fabulous high rate performance, can under 2.0 A/g multiplying powers
To realize fully charged/complete electric discharge, the energy density of corresponding 86.5 Wh/kg and the power density of 4400 W/kg in 1 minute；
Under 4.0 A/g high magnifications, the reversible capacity (attached drawing 7) of 35.7mAh/g still can get.
Embodiment 2
Configure electrolyte: in high-purity argon gas environment, by 0.313 g Zn (TFSI)2Zinc salt is dissolved in 1 mL AN, is sufficiently shaken
It swings, is completely dissolved salt, be configured to 0.5 mol/L Zn (TFSI)2- AN electrolyte.
Battery assembly: it is positive with the graphite positive plate work prepared in high-purity argon gas environment, the 0.5 of above-mentioned configuration
mol/L Zn(TFSI)2- AN solution makees electrolyte, and the metallic zinc foil cut makees cathode, with a thickness of the glass fibre of 0.2 mm
Film successively stacks, group as diaphragm according to the sequence of negative electrode casing, cathode, diaphragm, electrolyte, anode, gasket, elastic slice, anode cover
At laminated construction, 80 μ L electrolyte manufactured in the present embodiment are added dropwise on diaphragm between a positive electrode and a negative electrode infiltrates diaphragm, compacting
Encapsulation, zinc-base battery can be filled by being made.Gained electrolyte, battery are tested for the property.
Zinc-base battery manufactured in the present embodiment can stablize circulation, can provide about 40 under 50 mA/g current densities
The capacity of mAh/g, coulombic efficiency are about 90%.
Embodiment 3
Configure electrolyte: in high-purity argon gas environment, by 1.25 g Zn (TFSI)2Zinc salt is dissolved in 1 mL AN, is fullyd shake,
It is completely dissolved salt, is configured to 2 mol/L Zn (TFSI)2- AN electrolyte.
Battery assembly: in high-purity argon gas environment, make anode, 2 mol/ of above-mentioned configuration with the graphite positive plate prepared
L Zn(TFSI)2- AN solution makees electrolyte, and the metallic zinc foil cut makees cathode, makees with a thickness of the glass fibre membrane of 0.2 mm
It for diaphragm, successively stacks, organizes stacked according to the sequence of negative electrode casing, cathode, diaphragm, electrolyte, anode, gasket, elastic slice, anode cover
Layer structure, 80 μ L electrolyte manufactured in the present embodiment are added dropwise on diaphragm between a positive electrode and a negative electrode infiltrates diaphragm, compacting envelope
Dress, zinc-base battery can be filled by being made.Gained electrolyte, battery are tested for the property.
Zinc-base battery manufactured in the present embodiment can stablize circulation, can provide about 45 under 50 mA/g current densities
The capacity of mAh/g.
Embodiment 4
Configure electrolyte: in high-purity argon gas environment, by 0.125 g Zn (TFSI)2Zinc salt is dissolved in 1 mL PC, is sufficiently shaken
It swings, is completely dissolved salt, be configured to 0.2 mol/L Zn (TFSI)2- PC electrolyte.
Battery assembly: in high-purity argon gas environment, making anode with the graphite positive plate prepared, above-mentioned configuration
0.2mol/L Zn(TFSI)2- PC solution makees electrolyte, and the above-mentioned negative electrode tab prepared with zinc powder makees cathode, with a thickness of 0.2 mm's
Glass fibre membrane as diaphragm, successively according to negative electrode casing, cathode, diaphragm, electrolyte, anode, gasket, elastic slice, anode cover it is suitable
Sequence successively stacks, and forms laminated construction, 80 μ L electrolyte manufactured in the present embodiment are added dropwise on diaphragm between a positive electrode and a negative electrode to be made
Diaphragm infiltration, compacting encapsulation, zinc-base battery can be filled by being made.
Zinc-base battery manufactured in the present embodiment can be stablized using more than 300 charge and discharge, under 50 mA/g current densities
The about capacity of 42mAh/g can be provided, coulombic efficiency is about 92%.
Embodiment 5
Configure electrolyte: in high-purity argon gas environment, by 0.625 g Zn (PF6)2Zinc salt is dissolved in 1 mL TMP, is sufficiently shaken
It swings, is completely dissolved salt, be configured to 1 mol/L Zn (PF6)2- TMP electrolyte.
Battery assembly: in high-purity argon gas environment, make anode, 1 mol/ of above-mentioned configuration with the graphite positive plate prepared
L Zn(PF6)2- TMP solution makees electrolyte, and the above-mentioned negative electrode tab prepared with zinc powder makees cathode, with a thickness of the glass fibre of 0.2 mm
Film successively stacks, group as diaphragm according to the sequence of negative electrode casing, cathode, diaphragm, electrolyte, anode, gasket, elastic slice, anode cover
At laminated construction, 80 μ L electrolyte manufactured in the present embodiment are added dropwise on diaphragm between a positive electrode and a negative electrode infiltrates diaphragm, compacting
Encapsulation, zinc-base battery can be filled by being made.
Zinc-base battery manufactured in the present embodiment can be stablized using more than 300 charge and discharge, in 100 mA/g current densities
The about capacity of 35mAh/g can be provided down, and coulombic efficiency is about 93%.
Embodiment 6
Configure electrolyte: in high-purity argon gas environment, by 1.56 g Zn (TFSI)2Zinc salt is dissolved in 1 mL TEP, is sufficiently shaken
It swings, is completely dissolved salt, be configured to 2.5 mol/L Zn (TFSI)2- TEP electrolyte.
Battery assembly: in high-purity argon gas environment, making anode with the graphite positive plate prepared, above-mentioned configuration
2.5mol/L Zn(TFSI)2- TEP solution makees electrolyte, and the above-mentioned negative electrode tab prepared with zinc powder makees cathode, with a thickness of 0.2 mm
Glass fibre membrane as diaphragm, according to the sequence of negative electrode casing, cathode, diaphragm, electrolyte, anode, gasket, elastic slice, anode cover
Successively stack, form laminated construction, be added dropwise on diaphragm between a positive electrode and a negative electrode 80 μ L electrolyte manufactured in the present embodiment make every
Film infiltration, compacting encapsulation, zinc-base battery can be filled by being made.
Zinc-base battery manufactured in the present embodiment can be stablized using more than 500 charge and discharge, in 100 mA/g current densities
The about capacity of 40mAh/g can be provided down, and coulombic efficiency is about 97%.
Comparative example 1
Configure electrolyte: in high-purity argon gas environment, by 0.625 g Zn (TFSI)2Zinc salt is dissolved in 1 mL aqueous solvent, sufficiently
Concussion, is completely dissolved salt, is configured to 1 mol/L Zn (TFSI)2-H2O electrolyte.
Battery assembly: in high-purity argon gas environment, make anode, 1 mol/ of above-mentioned configuration with the graphite positive plate prepared
L Zn(TFSI)2-H2O solution makees electrolyte, and the metallic zinc foil cut makees cathode, makees with a thickness of the glass fibre membrane of 0.2 mm
For diaphragm, successively successively stacked according to the sequence of negative electrode casing, cathode, diaphragm, electrolyte, anode, gasket, elastic slice, anode cover, group
At laminated construction, the electrolyte that the preparation of 80 μ this comparative example of L is added dropwise on diaphragm between a positive electrode and a negative electrode infiltrates diaphragm, suppresses
Encapsulation, zinc-base battery can be filled by being made.
Gained electrolyte, battery are tested for the property.The result shows that the electrolyte of this comparative example preparation is in 2 V or less
It just decomposes, therefore zinc-base battery of the invention cannot carry out reversible fill in aqueous electrolyte prepared by this comparative example
Discharge of electricity.
Claims (10)
1. a kind of for the electrolyte of zinc-base battery, including soluble zinc salt and organic solvent can be filled, which is characterized in that it is described can
Soluble zinc salt is Zn (TFSI)2Or Zn (PF6)2, and the concentration of the soluble zinc salt is 0.2 ~ 2.5 mol/L；It is described organic molten
Agent is one of acetonitrile, propene carbonate, trimethyl phosphate and triethyl phosphate or any several.
2. according to claim 1 for the electrolyte of zinc-base battery can be filled, which is characterized in that the soluble zinc salt
Concentration is 0.5 ~ 2 mol/L.
3. according to claim 1 for the electrolyte of zinc-base battery can be filled, which is characterized in that the organic solvent is second
Nitrile.
4. according to claim 1 for the electrolyte of zinc-base battery can be filled, which is characterized in that the electrolyte can be used
Following methods are made: in high-purity argon gas environment, the soluble zinc salt electrolytic salt being completely dissolved in organic solvent, is made described
The concentration of soluble zinc salt is 0.2 ~ 2.5 mol/L, is uniformly mixed to being completely dissolved to obtain the final product.
5. one kind can fill zinc-base battery, including anode, cathode and electrolyte, which is characterized in that described just extremely graphite is positive, institute
Stating cathode is zinc load；The electrolyte includes soluble zinc salt and organic solvent.
6. according to claim 5 fill zinc-base battery, which is characterized in that it include lamellar graphite in the graphite anode,
Layered graphite includes layered conductive graphite and/or flakey electrically conductive graphite.
7. according to claim 5 fill zinc-base battery, which is characterized in that the graphite anode is by graphite and binder
It is evenly applied on collector after being mixed and made into slurry and obtained after drying.
8. according to claim 5 fill zinc-base battery, which is characterized in that the soluble zinc salt is Zn (TFSI)2Or Zn
(PF6)2, and the concentration of the soluble zinc salt is 0.2 ~ 2.5 mol/L.
9. according to claim 5 fill zinc-base battery, which is characterized in that the organic solvent is acetonitrile, propylene carbonate
One of ester, trimethyl phosphate and triethyl phosphate are any several.
10. filling the preparation method of zinc-base battery described in a kind of claim 5, which is characterized in that in high-purity argon gas environment,
It is successively stacked according to the sequence of negative electrode casing, zinc load, diaphragm, electrolyte, graphite anode, gasket, elastic slice, anode cover, Xiang Suoshu
The electrolyte is added dropwise on diaphragm makes its complete wetting, encapsulate battery to get.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910792425.3A CN110518295A (en) | 2019-08-26 | 2019-08-26 | One kind can fill zinc-base battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910792425.3A CN110518295A (en) | 2019-08-26 | 2019-08-26 | One kind can fill zinc-base battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN110518295A true CN110518295A (en) | 2019-11-29 |
Family
ID=68626914
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910792425.3A Pending CN110518295A (en) | 2019-08-26 | 2019-08-26 | One kind can fill zinc-base battery |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110518295A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112038683A (en) * | 2020-09-14 | 2020-12-04 | 西南大学 | Liquid organic zinc battery and application thereof |
| CN112164802A (en) * | 2020-09-30 | 2021-01-01 | 国网上海市电力公司 | Application of metal material and zinc-based battery taking metal as negative electrode |
| WO2023044969A1 (en) * | 2021-09-24 | 2023-03-30 | 天津大学 | Zinc-based electrochemical energy storage device |
| DE102022116245A1 (en) | 2022-06-29 | 2024-01-04 | Technische Universität Dresden | Electrolyte solution for high performance rechargeable batteries and capacitors |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105958131A (en) * | 2016-06-20 | 2016-09-21 | 南开大学 | Rechargeable water system zinc ion battery with long cycle life and high energy density |
| CN107634266A (en) * | 2017-08-18 | 2018-01-26 | 上海交通大学 | A kind of MH secondary battery flame-retardant electrolyte |
| CN108172833A (en) * | 2017-12-26 | 2018-06-15 | 深圳先进技术研究院 | Zinc-base Dual-ion cell and preparation method thereof |
| CN108242560A (en) * | 2017-12-26 | 2018-07-03 | 深圳先进技术研究院 | Zinc-base Dual-ion cell and preparation method thereof |
| CN109741967A (en) * | 2018-12-14 | 2019-05-10 | 中国科学院青岛生物能源与过程研究所 | A kind of hybrid super capacitor based on graphite anode and zinc load |
-
2019
- 2019-08-26 CN CN201910792425.3A patent/CN110518295A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105958131A (en) * | 2016-06-20 | 2016-09-21 | 南开大学 | Rechargeable water system zinc ion battery with long cycle life and high energy density |
| CN107634266A (en) * | 2017-08-18 | 2018-01-26 | 上海交通大学 | A kind of MH secondary battery flame-retardant electrolyte |
| CN108172833A (en) * | 2017-12-26 | 2018-06-15 | 深圳先进技术研究院 | Zinc-base Dual-ion cell and preparation method thereof |
| CN108242560A (en) * | 2017-12-26 | 2018-07-03 | 深圳先进技术研究院 | Zinc-base Dual-ion cell and preparation method thereof |
| CN109741967A (en) * | 2018-12-14 | 2019-05-10 | 中国科学院青岛生物能源与过程研究所 | A kind of hybrid super capacitor based on graphite anode and zinc load |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112038683A (en) * | 2020-09-14 | 2020-12-04 | 西南大学 | Liquid organic zinc battery and application thereof |
| CN112038683B (en) * | 2020-09-14 | 2023-01-24 | 西南大学 | Liquid organic zinc battery and application thereof |
| CN112164802A (en) * | 2020-09-30 | 2021-01-01 | 国网上海市电力公司 | Application of metal material and zinc-based battery taking metal as negative electrode |
| WO2023044969A1 (en) * | 2021-09-24 | 2023-03-30 | 天津大学 | Zinc-based electrochemical energy storage device |
| DE102022116245A1 (en) | 2022-06-29 | 2024-01-04 | Technische Universität Dresden | Electrolyte solution for high performance rechargeable batteries and capacitors |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1333475C (en) | Active material for cell and preparing method | |
| CN110518295A (en) | One kind can fill zinc-base battery | |
| CN111477957A (en) | Lithium metal battery electrolyte containing composite additive and preparation method thereof | |
| CN108844878A (en) | Negative pole piece, method for testing active specific surface area of pole piece and battery | |
| JP2008034368A (en) | Lithium ion storage battery containing contains tio2-b as anode active substance | |
| US11211635B2 (en) | Battery, battery pack, and uninterruptible power supply | |
| CN104795564B (en) | A kind of positive electrode of Aqueous solution secondary battery, pole piece, secondary cell and purposes | |
| CN108232161A (en) | A kind of full battery of sodium ion | |
| CN110034283A (en) | Phosphorization tin composite material and preparation method and application | |
| CN106848218A (en) | A kind of silicon or silicon alloy composite lithium ion battery cathode material containing biethyl diacid lithium borate and its preparation method and application | |
| CN101297420A (en) | High-capacity electrode active material for secondary battery | |
| CN110335764A (en) | A kind of pre- sodium modification method for efficiently constructing sodium ion capacitor | |
| CN112234195A (en) | Chargeable and dischargeable water system zinc ion full cell | |
| CN114373982A (en) | Liquid ether organic electrolyte-based less-negative-electrode secondary sodium battery and preparation method thereof | |
| CN115679380A (en) | Preparation method and application of crystal face oriented metal zinc | |
| CN113036100B (en) | Lithium metal composite negative electrode containing rigid particle framework and preparation method thereof | |
| CN114613980A (en) | Zinc ion battery composite negative electrode and preparation method and application thereof | |
| CN108539188A (en) | A kind of preparation method of liquid metal nano-particle and the preparation method of lithium ion battery | |
| CN112242570B (en) | Application of mixture of carbon material and ionic bromide and aqueous zinc-bromine double-ion battery | |
| CN116864781A (en) | Lithium-sodium mixed ion battery and preparation method thereof | |
| CN105609771A (en) | Nitrogen-doped multi-porous carbon negative electrode material and preparation method and application thereof | |
| CN108448095A (en) | A kind of sodium ion battery electrode material KTiOPO4Synthesis and application | |
| CN110482516B (en) | Positive electrode for rechargeable zinc-based battery and rechargeable zinc-based battery | |
| CN112467233A (en) | High-performance aqueous electrolyte for chargeable and dischargeable zinc-manganese battery | |
| JPH08124597A (en) | Solid electrolytic secondary cell |
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 | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20191129 |
|
| RJ01 | Rejection of invention patent application after publication |