CN107871849A - A kind of negative material suitable for water system sodium-ion battery - Google Patents
A kind of negative material suitable for water system sodium-ion battery Download PDFInfo
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- CN107871849A CN107871849A CN201710340327.7A CN201710340327A CN107871849A CN 107871849 A CN107871849 A CN 107871849A CN 201710340327 A CN201710340327 A CN 201710340327A CN 107871849 A CN107871849 A CN 107871849A
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- Prior art keywords
- ion battery
- water system
- negative
- sodium
- negative material
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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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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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
- H01M10/05—Accumulators with non-aqueous electrolyte
-
- 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
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
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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
- 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
- H01M4/5805—Phosphides
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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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/621—Binders
- H01M4/622—Binders being polymers
- H01M4/623—Binders being polymers fluorinated polymers
-
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
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- 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 present invention relates to a kind of negative material suitable for water system sodium-ion battery, belong to field of batteries.Negative material includes：Sodium ion embedded type compound, liberation of hydrogen inhibitor, binding agent and conductive material；The ion embedded type compound is NASICON structural compounds, selected from LiTi2(PO4)3Or NaTi2(PO4)3At least one of, shared part by weight is 70~80% in negative pole；The liberation of hydrogen inhibitor is selected from least one of bismuth sulfide or tin oxide, and shared part by weight is 2~10% in negative pole.The water system sodium-ion battery assembled with this negative material, has the characteristics that electrochemical energy high, service life length, good cycle, and charging upper limit voltage can keep good electrochemistry cycle performance close to can still keep high coulombic efficiency during 2.0V.
Description
Technical field
The present invention relates to a kind of negative material suitable for water system sodium-ion battery, belong to field of batteries.
Background technology
Social economy is also improving constantly in high speed development, the mankind to the interdependency of the energy.According to statistics, the present world
The 70% of annual energy resource consumption total amount derives from fossil energy (oil, coal, natural gas).But the burning of fossil fuel can produce greatly
The harmful substance of amount, not only pollutes the environment, and also serious threat the survival and development of human society.So human society face
The primary problem faced is to change irrational energy resource structure, while the energy for wanting Devoting Major Efforts To Developing to clean, and progressively to replace fossil energy
Source.Developing solar energy, wind energy, geothermal energy, this kind of reproducible clean energy resource of tide energy turns into the heat of current every country concern
Point.Regenerative resource is had a great influence by weather and period, have the characteristics that it is obvious unstable, discontinuous and uncontrollable,
Need to develop and build supporting energy storage device to ensure the stability for generating electricity, powering.Therefore, extensive energy storage skill
Art is to greatly develop the key of the renewable energy utilizations such as solar energy, wind energy and intelligent grid.
The energy storage technology of current main-stream mainly includes the energy storage of physics class and electrochemical energy storage, and wherein electrochemical energy storage has effect
Rate height, small investment, it is safe to use, using it is flexible the advantages that, very extensive research and application have been obtained, before there is good development
Scape.At present, lithium ion battery is the good high-energy battery system of development prospect, with energy density is big, discharge voltage is high, puts certainly
Electric rate is low, environment-friendly, the advantages that having extended cycle life.But with the large-scale application of lithium ion battery, the demand meeting of lithium
It is increasing, due to reserves limited in the earth's crust, cause the price of lithium material can more and more higher.Because sodium and lithium are in same master
Race, there are similar electrochemical properties, and rich reserves of the sodium in the earth's crust, account for 2.74%, be the 6th abundant element, sodium
Base battery is expected to the alternative as lithium ion battery.It is the same with lithium ion battery as the energy storage system of a new generation, safety
Sex chromosome mosaicism is the emphasis that we pay close attention to.Select different sodium salts and organic solvent and electrolyte is optimized, all can be to battery
Useful life, security performance and cycle performance produce certain influence.For lithium ion battery, the electricity of organic solvent class
Solution liquid achieves actual application in the battery of commercialization, but safety issue is always to restrict lithium ion battery development
Problem.This is primarily due to the flash-point of organic solvent than relatively low, inflammable, causes battery to be put etc. under extreme case overcharging, cross
The safety problem such as generation blast or burning.
The negative material cycle performance for water system sodium-ion battery that existing patent provides is poor, by hydrogen-evolution overpotential
Influence, capacity is often relatively low.This significantly impacts application of the water system sodium-ion battery under actual condition.
The content of the invention
For the deficiency of existing water system anode material of lithium-ion battery, it is an object of the invention to provide one kind to be applied to water
It is the negative material of sodium-ion battery, the negative pole has high power capacity ratio, long circulation life, the spies such as raw material sources are extensive, price is low
Point.
The technical scheme is that：
A kind of negative material suitable for water system sodium-ion battery, the negative material include：Sodium ion embedded type compound,
Liberation of hydrogen inhibitor, binding agent and conductive material；The ion embedded type compound is NASICON structural compounds, selected from LiTi2
(PO4)3Or NaTi2(PO4)3At least one of, shared part by weight is 70~80% in negative pole；The liberation of hydrogen inhibitor choosing
At least one of autovulcanization bismuth or tin oxide, shared part by weight is 2~10% in negative pole.
The binding agent is at least one of polytetrafluoroethylene (PTFE), Kynoar, water-soluble rubber and cellulose.
The binding agent shared part by weight in negative pole is 1~10%.
The conductive material is at least one of acetylene black, graphite, carbon black, conducting polymer.
The conductive material shared part by weight in negative pole is 1~10%.
The negative material has effective specific capacity Reversible Cycle more than 50mAh/g.
Advantages of the present invention and beneficial effect are：
1st, the present invention assembles water system sodium-ion battery by the use of this material as negative pole, it is contemplated that cost and security, adopts
With λ-MnO2As cell positive material, barrier film uses the existing porous polyphenyl alkene barrier film to use for nickel-hydrogen battery, and electrolyte solution is adopted
With 1mol/L sodium sulphate, cyclicity that the full battery after assembling overcomes water system sodium-ion battery in previous patent is poor, specific capacity
The problem of low.
2nd, negative material mature preparation process involved in the present invention, production cost is relatively low, stable circulation, and specific capacity is high, and ten
Divide the negative material for being suitable as water system sodium-ion battery, have by the water system sodium-ion battery that negative pole assembles of this electrode material
There is the characteristics of long cycle life, high energy ratio, low cost and non-environmental-pollution.
Embodiment
In specific implementation process, the present invention is applied to the negative material of water system sodium-ion battery, and negative pole includes：Sodium ion
Embedded type compound, liberation of hydrogen inhibitor, binding agent and conductive material.The ion embedded type compound is NASICON structurings
Compound, selected from LiTi2(PO4)3Or NaTi2(PO4)3At least one of, in negative pole proportion be preferably 72~
78wt%.The liberation of hydrogen inhibitor is selected from least one of bismuth sulfide or tin oxide, in negative pole proportion be preferably 2~
8wt%.Liberation of hydrogen inhibitor can lift negative pole overpotential of hydrogen evolution, so that negative pole drops to lower current potential in charging, ensure
Battery has higher operating voltage, is advantageous to improve battery cycle life and coulombic efficiency.The binding agent is polytetrafluoroethyl-ne
At least one of alkene, Kynoar, water-soluble rubber and cellulose, proportion is preferably 5~10wt% in negative pole.
The conductive material is at least one of acetylene black, graphite, carbon black, conducting polymer, and proportion is preferably 5 in negative pole
~10wt%.Above-mentioned four kinds of materials are mixed in certain mass ratio, uniform, the sticking mixing material of tool is made, passes through pressure
Power or conducting resinl are fixed on a current collector, and collector includes stainless steel, nickel, titanium, aluminium, graphite fiber cloth etc..
The present invention is discussed in detail for specific embodiment below, there is provided embodiment is for the ease of understanding the present invention, is definitely not
The limitation present invention.
Embodiment 1
In the present embodiment, negative material is according to NaTi2(PO4)3：Bismuth sulfide：Acetylene black：PVDF binding agent=75：5：10：
10 part by weight mixed slurry, is evenly applied on nickel screen collector, and the thick electrode slices of 0.4mm are pressed into after drying.Positive pole
Composition is according to λ-MnO2：Acetylene black：PVDF binding agent=80：10：10 part by weight mixed slurry, is evenly applied to nickel screen collection
The thick electrode slices of 0.4mm are pressed on fluid, after drying.Using analytically pure raw material, 1.0mol/L sodium sulphate electrolyte is configured.
Both positive and negative polarity electrode is cut according to specification, using the barrier film of commercial Ni-MH battery and the electrolyte of above-mentioned configuration, pairing is assembled into
Battery.Charge and discharge cycles test is carried out with 40mA/g current strength in 0~1.8V operating voltages section.First discharge specific capacity is
70.1mAh/g, efficiency is 89.8% first, after 200 circulations, capability retention 91.2%.
Embodiment 2
In the present embodiment, negative material is according to NaTi2(PO4)3：Bismuth sulfide：Acetylene black：PVDF binding agent=78：2：10：
10 part by weight mixed slurry, is evenly applied on nickel screen collector, and the thick electrode slices of 0.4mm are pressed into after drying.Positive pole
Composition is according to λ-MnO2：Acetylene black：PVDF binding agent=80：10：10 part by weight mixed slurry, is evenly applied to nickel screen collection
The thick electrode slices of 0.4mm are pressed on fluid, after drying.Using analytically pure raw material, 1.0mol/L sodium sulphate electrolyte is configured.
Both positive and negative polarity electrode is cut according to specification, using the barrier film of commercial Ni-MH battery and the electrolyte of above-mentioned configuration, pairing is assembled into
Battery.Charge and discharge cycles test is carried out with 40mA/g current strength in 0~1.8V operating voltages section.First discharge specific capacity is
58.1mAh/g, efficiency is 83.8% first, after 200 circulations, capability retention 92.9%.
Embodiment 3
In the present embodiment, negative material is according to NaTi2(PO4)3：Bismuth sulfide：Acetylene black：PVDF binding agent=72：8：10：
10 part by weight mixed slurry, is evenly applied on nickel screen collector, and the thick electrode slices of 0.4mm are pressed into after drying.Positive pole
Composition is according to λ-MnO2：Acetylene black：PVDF binding agent=80：10：10 part by weight mixed slurry, is evenly applied to nickel screen collection
The thick electrode slices of 0.4mm are pressed on fluid, after drying.Using analytically pure raw material, 1.0mol/L sodium sulphate electrolyte is configured.
Both positive and negative polarity electrode is cut according to specification, using the barrier film of commercial Ni-MH battery and the electrolyte of above-mentioned configuration, pairing is assembled into
Battery.Charge and discharge cycles test is carried out with 40mA/g current strength in 0~1.8V operating voltages section.First discharge specific capacity is
64.2mAh/g, efficiency is 86.3% first, after 200 circulations, capability retention 94.1%.
Embodiment result shows, the water system sodium-ion battery assembled with negative material of the present invention, have electrochemical energy it is high,
The features such as service life is long, good cycle, charging upper limit voltage, and can close to can still keep high coulombic efficiency during 2.0V
To keep good electrochemistry cycle performance.
Above-mentioned embodiment is to illustrate the features of the present invention, but the present invention is not limited to above-described embodiment,
In those of ordinary skill in the art's possessed knowledge, it can also be made on the premise of present inventive concept is not departed from
Various change, it also should be regarded as protection scope of the present invention.
Claims (6)
1. a kind of negative material suitable for water system sodium-ion battery, it is characterised in that the negative material includes：Sodium ion is embedded in
Type compound, liberation of hydrogen inhibitor, binding agent and conductive material；The ion embedded type compound is NASICON structural compounds,
Selected from LiTi2(PO4)3Or NaTi2(PO4)3At least one of, shared part by weight is 70~80% in negative pole；The analysis
Hydrogen inhibitor is selected from least one of bismuth sulfide or tin oxide, and shared part by weight is 2~10% in negative pole.
2. the negative material according to claim 1 suitable for water system sodium-ion battery, it is characterised in that the binding agent
For at least one of polytetrafluoroethylene (PTFE), Kynoar, water-soluble rubber and cellulose.
3. the negative material according to claim 1 suitable for water system sodium-ion battery, it is characterised in that the binding agent
Shared part by weight is 1~10% in negative pole.
4. the negative material according to claim 1 suitable for water system sodium-ion battery, it is characterised in that the conduction material
Expect at least one of acetylene black, graphite, carbon black, conducting polymer.
5. the negative material according to claim 1 suitable for water system sodium-ion battery, it is characterised in that the conduction material
Material shared part by weight in negative pole is 1~10%.
6. the negative material according to claim 1 suitable for water system sodium-ion battery, it is characterised in that the negative pole material
Material is with effective specific capacity Reversible Cycle more than 50mAh/g.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710340327.7A CN107871849A (en) | 2017-05-15 | 2017-05-15 | A kind of negative material suitable for water system sodium-ion battery |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710340327.7A CN107871849A (en) | 2017-05-15 | 2017-05-15 | A kind of negative material suitable for water system sodium-ion battery |
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| CN107871849A true CN107871849A (en) | 2018-04-03 |
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| CN201710340327.7A Pending CN107871849A (en) | 2017-05-15 | 2017-05-15 | A kind of negative material suitable for water system sodium-ion battery |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110862075A (en) * | 2019-10-15 | 2020-03-06 | 扬州扬达新能源有限公司 | Preparation method of cathode material of water-based sodium-ion battery |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103022577A (en) * | 2012-12-27 | 2013-04-03 | 武汉大学 | Water system chargeable sodium-ion battery |
| CN103597655A (en) * | 2011-06-15 | 2014-02-19 | 南加利福尼亚大学 | High efficiency iron electrode and additives for use in rechargeable iron-based batteries |
-
2017
- 2017-05-15 CN CN201710340327.7A patent/CN107871849A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103597655A (en) * | 2011-06-15 | 2014-02-19 | 南加利福尼亚大学 | High efficiency iron electrode and additives for use in rechargeable iron-based batteries |
| CN103022577A (en) * | 2012-12-27 | 2013-04-03 | 武汉大学 | Water system chargeable sodium-ion battery |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110862075A (en) * | 2019-10-15 | 2020-03-06 | 扬州扬达新能源有限公司 | Preparation method of cathode material of water-based sodium-ion battery |
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Application publication date: 20180403 |