CN108172911A - A kind of full vanadium Water-soluble lithium ion battery - Google Patents
A kind of full vanadium Water-soluble lithium ion battery Download PDFInfo
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- CN108172911A CN108172911A CN201810027413.7A CN201810027413A CN108172911A CN 108172911 A CN108172911 A CN 108172911A CN 201810027413 A CN201810027413 A CN 201810027413A CN 108172911 A CN108172911 A CN 108172911A
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- lithium
- lithium ion
- vanadium
- ion battery
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
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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
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
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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
- H01M4/48—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
-
- 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
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
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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
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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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
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
-
- 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
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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 full vanadium Water-soluble lithium ion batteries, belong to field of chemical power source.The lithium ion battery plus-negative plate active material is solid-state vanadium base intercalation materials of li ions, and wherein positive electrode is the rich lithium state vanadium based phosphates for having upper electrode potential, and negative material is the poor lithium state barium oxide for having relatively low electrode potential, and electrolyte is Aqueous Lithium Salts.When the battery works, the storage and conversion of energy are realized in lithium ion reversible embedded abjection in positive and negative anodes lattice.Compared to traditional all-vanadium flow battery, battery system proposed by the present invention has higher energy density, power-performance and cycle life, and can work within the scope of wider temperature, therefore has potential application prospect in extensive energy storage field.
Description
Technical field
The present invention relates to a kind of full vanadium Water-soluble lithium ion batteries, belong to field of chemical power source.
Background technology
Extensive energy storage is to efficiently use the technical foundation of natural energy resources, structure global energy internet.Wherein, lithium ion
Battery is because of series of advantages such as its high-energy density, long circulation life, high working voltage, memory-less effects, it is considered to be most has
The electrochemical energy storage system of development prospect.But lithium ion battery, since assembled condition is harsh, production cost is higher；Electrolyte is
Organic ignitable components, there are potential safety issues, this all limits the fast development of lithium ion battery.If by Organic Electricity
Solution liquid is substituted for aqueous solution, fundamentally solves the safety issue of lithium ion battery, and do not need to stringent mounting ring
Border has been greatly reduced production cost, is more in line with the application demand of extensive energy storage.But due to the electrochemical window by aqueous solution
The selectional restriction of mouth and material, current commercialized aqueous solution battery energy density are low, it is difficult to meet growing energy need
It asks；And aqueous solution thermal stable temperature range is not wide, it is difficult to applied under extensive environment temperature.All-vanadium flow battery is due to charge and discharge
Invertibity is high, have extended cycle life, energy conversion efficiency is high, positive and negative anodes electrolyte no cross contamination and quilt the advantages that easy scale
It is considered the water-soluble solution battery for having very much application value.But all-vanadium flow battery is that a kind of active material is in the oxygen for circulating liquid
Electrochemical cell, since the solubility of vanadium active material in the solution is certain so that its volume energy density and quality energy
Metric density is all relatively low；And the solubility of vanadium active material at low temperature is lower and high temperature under have the deposition analysis of vanadic anhydride
Go out so that its operating temperature range is 10~40 DEG C.If the all-vanadium flow battery of liquid energy storage is substituted for solid-state energy storage
Full vanadium Water-soluble lithium ion battery, volume energy density and mass energy density will all increase considerably；Simultaneously using highly concentrated
The lithium salt solution of degree can make it work in broader temperature range.Therefore, exploitation has excellent performance, is cheap, is safe
Full vanadium Water-soluble lithium ion battery, for clean energy resource it is efficient using and novel energy society smooth structure, meaning weight
Greatly.
Invention content
The object of the present invention is to provide a kind of full vanadium Water-soluble lithium ion batteries, close to solve the existing aqueous solution energy content of battery
It spends low and the problem of cannot be used under extensive environment temperature.
Technical scheme of the present invention can be realized by following technical measures：
A kind of full vanadium Water-soluble lithium ion battery, including anode, cathode and electrolyte, the anode, which uses, has higher electricity
As a positive electrode active material, the cathode uses the poor lithium state with relatively low electrode potential to the rich lithium state vanadium based phosphates of electrode potential
Barium oxide uses high concentration Aqueous Lithium Salts as negative electrode active material, the electrolyte.
Preferably, the anode composition includes：Positive active material, conductive agent and binding agent are uniformly mixed, then glued
It is connected on collector；The cathode composition includes：Negative electrode active material, conductive agent and binding agent are uniformly mixed, are then bonded
In on collector.
Preferably, the positive active material is phosphoric acid vanadium lithium (Li3V2(PO4)3), vanadyl phosphate lithium (LiVOPO4) and fluorine
For phosphoric acid vanadium lithium (LiVPO4F it is one or more in).
Preferably, the negative electrode active material is vanadium dioxide (VO2), lithium vanadate (LiV3O8) and vanadic anhydride (V2O5)
In it is one or more.
Preferably, the ratio between amount of substance of lithium salts and water is in the electrolyte：(0.1~0.55)：1.
Preferably, the lithium salts be bis trifluoromethyl sulfimide lithium (LiTFSI), trifluoromethyl sulfonic acid lithium (LiOTF),
Double fluorine sulfimide lithiums (LiFSI), lithium perchlorate (LiClO4) in it is one or more.
Preferably, the conductive agent is one or more in Ketjen black, acetylene black, micro crystal graphite and conductive black.
Preferably, the collector is one kind in titanium net, nickel foam, aluminium net, copper mesh, aluminium foil, copper foil and titanium foil.
Compared with prior art, the present invention has the advantages that：
When the battery works, the storage and conversion of energy are realized in lithium ion reversible embedded abjection in positive and negative anodes lattice.Phase
Than in traditional all-vanadium flow battery, battery system proposed by the present invention has higher energy density, power-performance and cycle
Service life, and can work within the scope of wider temperature, therefore there is potential application prospect in extensive energy storage field.
Description of the drawings
Using attached drawing, the invention will be further described, but the embodiment in attached drawing does not form any limit to the present invention
System.
Fig. 1 is the charging and discharging curve of battery (25 DEG C) at room temperature in embodiment 1；
Fig. 2 is the cycle performance figure of battery (25 DEG C) at room temperature in embodiment 2；
Fig. 3 is the cycle performance figure of battery (25 DEG C) at room temperature in embodiment 3；
Fig. 4 is charging and discharging curve of the battery at -20 DEG C, 25 DEG C and 80 DEG C in embodiment 4.
Specific embodiment
To make the present invention easier to understand, specific embodiments of the present invention are further illustrated below.
Embodiment 1
Present embodiment describes one kind with fluorophosphate vanadium lithium (LiVPO4F it is) anode, vanadic anhydride (V2O5) it is negative
Pole, the amount LiClO of substance4：Water=0.1：1 LiClO4Aqueous solution is the full vanadium Water-soluble lithium ion battery of electrolyte.
Anode portion：Take fluorophosphate vanadium lithium (LiVPO4F it is) positive electrode active materials, conductive black Super P are conduction
Carbon, 4% Kynoar (PVDF) is as binding agent, according to active material：Conductive carbon：Binding agent=8：1：1 mass ratio,
It is uniformly mixed, is applied on titanium foil, it is then 12 hours dry in 100 DEG C of vacuum drying ovens, as anode.
Cathode portion：Take vanadic anhydride (V2O5) it is negative electrode active material, acetylene black is made as conductive carbon, 4% PVDF
For binding agent, according to active material：Conductive carbon：Binding agent=8：1：1 mass ratio, is uniformly mixed, and is applied on aluminium foil,
Then it is 12 hours dry in 100 DEG C of vacuum drying ovens, as cathode.
Electrolyte：The amount LiClO of substance4：Water=0.1：1 LiClO4Aqueous solution.
Finally by positive and negative anodes according to active material quality 1:The 1 full battery of ratio match, the specific capacity of full battery is to be based on
Positive active material quality.
Fig. 1 is the charging and discharging curve figure of 1 gained battery of embodiment at room temperature, and test voltage ranging from 0.5~1.8V is electric
The specific capacity in pond is 98.5mAh/g.
Embodiment 2
Present embodiment describes one kind with phosphoric acid vanadium lithium (Li3V2(PO4)3) for anode, vanadium dioxide (VO2) for cathode, object
The amount LiOTF of matter：Water=0.396：1 LiOTF aqueous solutions are the full vanadium Water-soluble lithium ion battery of electrolyte.
Anode portion：Take phosphoric acid vanadium lithium (Li3V2(PO4)3) for positive electrode active materials, Ketjen black is conductive carbon, 60%
PTFE emulsion is as binding agent, according to active material：Conductive carbon：Binding agent=7：2：1 mass ratio, is uniformly mixed,
Film is rolled on roll squeezer, it is then 12 hours dry in 100 DEG C of vacuum drying ovens, it is finally pressed in aluminium net, as anode.
Cathode portion：Take vanadium dioxide (VO2) it is negative electrode active material, acetylene black is as conductive carbon, 60% PTFE breasts
Liquid is as binding agent, according to active material：Conductive carbon：Binding agent=7：2：1 mass ratio, is uniformly mixed, in roll squeezer
On be rolled into film, then dry 12 hours in 100 DEG C of vacuum drying ovens, be finally pressed on nickel foam, as cathode.
Electrolyte：The amount LiOTF of substance：Water=0.396：1 LiOTF aqueous solutions.
Finally by positive and negative anodes according to active material quality 1:The 1 full battery of ratio match, the specific capacity of full battery is to be based on
Positive active material quality.
Fig. 2 is the cycle performance figure of 2 gained battery of embodiment at room temperature, test voltage ranging from 0.5~1.8V, battery
Specific capacity for 81.9mAh/g, capacity retention ratio is 88% after cycle 100 weeks.
Embodiment 3
Present embodiment describes one kind with fluorophosphate vanadium lithium (LiVPO4F it is) anode, lithium vanadate (LiV3O8) it is cathode,
The amount LiTFSI of substance：LiOTF：Water=0.378：0.126：1 LiTFSI+LiOTF aqueous solutions are water-soluble for the full vanadium of electrolyte
Liquid lithium ion battery.
Anode portion：Take fluorophosphate vanadium lithium (LiVPO4F) for positive electrode active materials, Super P are conductive carbon, 4%
PVDF is as binding agent, according to active material：Conductive carbon：Binding agent=8：1：1 mass ratio, is uniformly mixed, and is applied to
It is then 12 hours dry in 100 DEG C of vacuum drying ovens on aluminium foil, as anode.
Cathode portion：Take lithium vanadate (LiV3O8) it is negative electrode active material, acetylene black is as conductive carbon, 4% PVDF conducts
Binding agent, according to active material：Conductive carbon：Binding agent=8：1：1 mass ratio, is uniformly mixed, and is applied on aluminium foil, so
It is 12 hours dry in 100 DEG C of vacuum drying ovens afterwards, as cathode.
Electrolyte：The amount LiTFSI of substance：LiOTF：Water=0.378：0.126：1 LiTFSI+LiOTF aqueous solutions.
Finally by positive and negative anodes according to active material quality 1:The 1 full battery of ratio match, the specific capacity of full battery is to be based on
Positive active material quality.
Fig. 3 is the cycle performance figure of 3 gained battery of embodiment at room temperature, test voltage ranging from 0.5~2V, battery
Specific capacity is 109.6mAh/g, and capacity retention ratio is 76% after cycle 100 weeks.
Embodiment 4
Present embodiment describes one kind with vanadyl phosphate lithium (LiVOPO4) for anode, vanadium dioxide (VO2) for cathode, substance
Amount LiTFSI：Water=0.378：1 LiTFSI aqueous solutions are the full vanadium Water-soluble lithium ion battery of electrolyte.
Anode portion：Take vanadyl phosphate lithium (LiVOPO4) for positive electrode active materials, Ketjen black is conductive carbon, 60%
PTFE emulsion is as binding agent, according to active material：Conductive carbon：Binding agent=7：2：1 mass ratio, is uniformly mixed,
Film is rolled on roll squeezer, it is then 12 hours dry in 100 DEG C of vacuum drying ovens, it is finally pressed in titanium net, as anode.
Cathode portion：Take vanadium dioxide (VO2) it is negative electrode active material, acetylene black is as conductive carbon, 4% PVDF lotions
As binding agent, according to active material：Conductive carbon：Binding agent=7：2：1 mass ratio, is uniformly mixed, on roll squeezer
Film is rolled into, it is then 12 hours dry in 100 DEG C of vacuum drying ovens, it is finally pressed in titanium net, as cathode.
Electrolyte：The amount LiTFSI of substance：Water=0.378：1 LiTFSI aqueous solutions.
Finally by positive and negative anodes according to active material quality 1:The 1 full battery of ratio match, the specific capacity of full battery is to be based on
Positive active material quality.
Fig. 4 is charging and discharging curve figure of the 4 gained battery of embodiment at -20 DEG C, 25 DEG C and 80 DEG C, and test voltage range is equal
For 0.5~1.8V, specific capacity of the battery at -20 DEG C, 25 DEG C and 80 DEG C is 55.8,118.3,131mAh/g.
Finally, it should be noted that the above embodiments are merely illustrative of the technical solutions of the present invention rather than the present invention is protected
The limitation of range is protected, although being explained in detail with reference to preferred embodiment to the present invention, those of ordinary skill in the art should
Understand, technical scheme of the present invention can be modified or replaced equivalently, without departing from the essence of technical solution of the present invention
And range.
Claims (8)
1. a kind of full vanadium Water-soluble lithium ion battery, which is characterized in that including anode, cathode and electrolyte, the anode uses
As a positive electrode active material, the cathode uses to be had compared with low electrode electricity rich lithium state vanadium based phosphates with upper electrode potential
The poor lithium state barium oxide of gesture uses high concentration Aqueous Lithium Salts as negative electrode active material, the electrolyte.
2. full vanadium Water-soluble lithium ion battery according to claim 1, which is characterized in that the anode composition includes：It will
Positive active material, conductive agent and binding agent are uniformly mixed, and are then adhered on collector；The cathode composition includes：It will be negative
Pole active material, conductive agent and binding agent are uniformly mixed, and are then adhered on collector.
3. full vanadium Water-soluble lithium ion battery according to claim 1, which is characterized in that the positive active material is phosphorus
Sour vanadium lithium (Li3V2(PO4)3), vanadyl phosphate lithium (LiVOPO4) and fluorophosphate vanadium lithium (LiVPO4F it is one or more in).
4. full vanadium Water-soluble lithium ion battery according to claim 1, which is characterized in that the negative electrode active material is two
Vanadium oxide (VO2), lithium vanadate (LiV3O8) and vanadic anhydride (V2O5) in it is one or more.
5. full vanadium Water-soluble lithium ion battery according to claim 1, which is characterized in that lithium salts and water in the electrolyte
The ratio between the amount of substance be：(0.1~0.55)：1.
6. full vanadium Water-soluble lithium ion battery according to claim 1, which is characterized in that the lithium salts is bis trifluoromethyl
Sulfimide lithium (LiTFSI), trifluoromethyl sulfonic acid lithium (LiOTF), double fluorine sulfimide lithiums (LiFSI), lithium perchlorate
(LiClO4) in it is one or more.
7. full vanadium Water-soluble lithium ion battery according to claim 2, which is characterized in that the conductive agent be Ketjen black,
It is one or more in acetylene black, micro crystal graphite and conductive black.
8. full vanadium Water-soluble lithium ion battery according to claim 2, which is characterized in that the collector is titanium net, bubble
One kind in foam nickel, aluminium net, copper mesh, aluminium foil, copper foil and titanium foil.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201810027413.7A CN108172911A (en) | 2018-01-11 | 2018-01-11 | A kind of full vanadium Water-soluble lithium ion battery |
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| CN201810027413.7A CN108172911A (en) | 2018-01-11 | 2018-01-11 | A kind of full vanadium Water-soluble lithium ion battery |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112838204A (en) * | 2021-01-07 | 2021-05-25 | 欣旺达电动汽车电池有限公司 | Negative electrode active material, preparation method thereof, negative electrode material, negative electrode sheet and battery |
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| CN112838204A (en) * | 2021-01-07 | 2021-05-25 | 欣旺达电动汽车电池有限公司 | Negative electrode active material, preparation method thereof, negative electrode material, negative electrode sheet and battery |
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