CN108711636A - A kind of combination electrolyte double ion rocking chair type secondary cell and preparation method thereof - Google Patents
A kind of combination electrolyte double ion rocking chair type secondary cell and preparation method thereof Download PDFInfo
- Publication number
- CN108711636A CN108711636A CN201810556847.6A CN201810556847A CN108711636A CN 108711636 A CN108711636 A CN 108711636A CN 201810556847 A CN201810556847 A CN 201810556847A CN 108711636 A CN108711636 A CN 108711636A
- Authority
- CN
- China
- Prior art keywords
- electrolyte
- rocking chair
- type secondary
- secondary cell
- chair type
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- 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
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0568—Liquid materials characterised by the solutes
-
- 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
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0569—Liquid materials characterised by the solvents
-
- 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 discloses a kind of combination electrolyte double ion rocking chair type secondary cells and preparation method thereof, belong to electrochemical storage technical field.The battery of the present invention includes anode, cathode, diaphragm and electrolyte, and electrolyte includes anode electrolyte and electrolyte liquid, and anode electrolyte is the ionic liquid containing alkali metal salt, and electrolyte liquid is the ether organic solvent containing identical alkali metal salt；Positive and negative electrode instills corresponding anode electrolyte and electrolyte liquid in diaphragm both sides respectively by membranes apart.The present invention also provides the preparation methods of the battery, include the following steps：Positive electrode, negative material and diaphragm are processed into slabbing；Anode electrolyte and electrolyte liquid are added dropwise respectively in diaphragm both sides, obtains combination electrolyte double ion rocking chair type secondary cell.The advantages of combination electrolyte double ion rocking chair type secondary cell of the present invention can play anode electrolyte and electrolyte liquid simultaneously, to which the cyclical stability of battery be greatly improved.
Description
Technical field
The present invention relates to a kind of combination electrolyte double ion rocking chair type secondary cells and preparation method thereof, belong to electrochemistry
Technical field of memory.
Background technology
Lithium ion battery is one of most important energy storage device in the world today, the carrier that it transmits lithium ion as charge
Deintercalation is in just between negative material, and to reach power storage and release, it has, and energy density is high, power density it is high and
The advantages that operating voltage is high has broad application prospects in extensive energy storage and traffic transport industry.It is closed in lithium ion battery
Key raw material elemental lithium, reserves only have 0.065% in the earth's crust, and are unevenly distributed, and are concentrated mainly on South American region.With the world
Expanding economy, the demand of the mankind lived with production to lithium resource, which can be measured, to be continued to increase, it is anticipated that the price of lithium resource will
It can rise steadily therewith, this will cause various lithium electronic apparatus applications difficult and expensive, therefore develop new type of energy storage device
It is very urgent to substitute lithium ion battery energy storage device.Compared with lithium ion battery, negative and positive double ion rocking chair type battery passes through
Two kinds of ions of negative and positive between positive and negative pole material, have output voltage high, environmental-friendly and cheap etc. as carrier deintercalation
Advantage, it is considered to be one of most promising next generation's new type of energy storage device.But it is positive in negative and positive double ion rocking chair type battery
During the deintercalation for reacting anion, reaction potential is in 5V or so, traditional organic electrolyte meeting under so high current potential
Serious oxygenolysis occurs, to which the stability and efficiency sharp-decay of battery can be caused.Therefore there is scientist's trial in the recent period
Using the ionic liquid with good antioxidant properties its as battery electrolyte, result of study show ionic liquid be use
Really the decomposition that can effectively inhibit electrolyte, improves the cathode performance of battery.Although this measure ensures anode well
Reaction, but also brings some series of problems, especially the use of il electrolyte its can influence negative material surface
The serious side reaction that unstable solid electrolyte membrane causes cathode is produced, lowers battery coulombic efficiency significantly, influences battery
Cyclical stability.The positive and negative anodes reaction for how effectively designing negative and positive double ion rocking chair type battery, ensures that negative and positive double ion shakes
Chair form battery high output voltage, environmental-friendly and inexpensive etc. advantages, push its commercialization, be always perplex scientist together
Problem.
Invention content
In order to solve the above technical problems, the object of the present invention is to provide a kind of combination electrolyte double ion rocking chair type is secondary
Battery and preparation method thereof, combination electrolyte double ion rocking chair type secondary cell of the invention use ion in anode reacts
Liquid is that electrolyte ensures that electrolyte is not decomposed under high working voltage, and it is electricity that ether organic solvent is used in negative reaction
The advantages of solving the coulombic efficiency that liquid ensures cathode, anode electrolyte and electrolyte liquid can be played simultaneously, to be greatly improved
The cyclical stability of battery.
The first purpose of the invention is to provide a kind of double ion rocking chair type secondary cells, including positive electrode, cathode material
Material, diaphragm and electrolyte, the electrolyte are combined electrolyte, including anode electrolyte and electrolyte liquid, the anode
Electrolyte is the ionic liquid containing alkali metal salt, and the electrolyte liquid is that the ethers containing identical alkali metal salt is organic molten
Agent.
In one embodiment of the invention, the anion in the anion and alkali metal salt in the ionic liquid is protected
It holds consistent.
In one embodiment of the invention, the cation in the alkali metal salt is selected from Li+、Na+Or K+, the alkali
Anion in metal salt is selected from bis- (fluoroform) sulfimide roots, bis- (fluorine sulphonyl) imines roots, trifluoromethanesulfonic acid root or six
Fluorophosphoric acid root.
In one embodiment of the invention, the cation in the ionic liquid is selected from 1- methyl-1s-propyl pyrrole
Alkane ion, 1- ethyl-3-methylimidazoles ion, N- trimethoxy silicon substrate propyl-N, N, N- trimethyl cations or N, N- dioxane
Base pyrrolidinium ions.
In one embodiment of the invention, the ionic liquid is 1- methyl-1s-bis- (fluoroforms of propyl pyrrole alkane
Alkane) sulfimide, bis- (fluoroform) sulfimides of 1- ethyl-3-methylimidazoles, N- trimethoxy silicon substrate propyl-N, N, N- tri-
Bis- (fluoroform) sulfimides of methyl, N, bis- (fluoroform) sulfimides of N- dialkyl pyrrolidiniums, 1- methyl-1s-propyl
Bis- (fluorine sulphonyl) imines of pyrrolidines, bis- (fluorine sulphonyl) imines of 1- ethyl-3-methylimidazoles, N- trimethoxy silicon substrate propyl-N, N,
Bis- (fluorine sulphonyl) imines of N- trimethyls, N, bis- (fluorine sulphonyl) imines of N- dialkyl pyrrolidiniums, 1- methyl-1s-propyl pyrrole alkane three
Fluorine methanesulfonic acid, 1- ethyl-3-methylimidazoles trifluoromethanesulfonic acid, N- trimethoxy silicon substrate propyl-N, N, N- trimethyl trifluoro methylsulphurs
Acid, N, N- dialkyl pyrrolidiniums trifluoromethanesulfonic acid, 1- methyl-1s-propyl pyrrole alkane hexafluorophosphoric acid, 1- ethyl-3-methylimidazoles
Hexafluorophosphoric acid, N- trimethoxy silicon substrate propyl-N, N, N- trimethyl hexafluorophosphoric acids or N, N- dialkyl pyrrolidinium hexafluorophosphoric acid.
In one embodiment of the invention, the alkali metal salt is bis- (fluoroform) sulfimide lithiums, bis- (fluorine sulphurs
Acyl) imine lithium, trifluoromethanesulfonic acid lithium, lithium hexafluoro phosphate, bis- (fluoroform) sulfimide sodium, bis- (fluorine sulphonyl) imines sodium, three
Fluorine methanesulfonic sodium, sodium hexafluoro phosphate, bis- (fluoroform) sulfimide potassium, bis- (fluorine sulphonyl) imines potassium, trifluoromethanesulfonic acid potassium or
Potassium Hexafluorophosphate.
In one embodiment of the invention, ether organic solvent be diethylene glycol dimethyl ether, triethylene glycol dimethyl ether,
One or more of tetraethyleneglycol dimethyl ether and five ethylene glycol dimethyl ether.
In one embodiment of the invention, a concentration of 0.1-10mol L of anode electrolyte-1.Preferably, electrolyte
A concentration of 1.5mol L-1。
In one embodiment of the invention, a concentration of 0.1-10mol L of electrolyte liquid-1.Preferably, electrolyte
A concentration of 2.75mol L-1。
In one embodiment of the invention, the positive electrode is carbon materials.
In one embodiment of the invention, the carbon materials are graphite, mesoporous carbon, hard carbon or soft carbon.
In one embodiment of the invention, the positive electrode further includes binder.
In one embodiment of the invention, the binder is Kynoar, polytetrafluoroethylene (PTFE), carboxymethyl cellulose
One or more of plain sodium, polyolefin, SBR rubber, Viton and Polyurethane.
In one embodiment of the invention, the negative material is carbon materials or lithium metal, metallic sodium, metal
Potassium, silicon, tin, aluminium, phosphorus or lithium titanate.
In one embodiment of the invention, the carbon materials are graphite, mesoporous carbon, hard carbon or soft carbon.
In one embodiment of the invention, when negative material is carbon materials, negative material further includes binder.
In one embodiment of the invention, binder is Kynoar, polytetrafluoroethylene (PTFE), carboxymethyl cellulose
One or more of sodium, polyolefin, SBR rubber, Viton and Polyurethane.
In one embodiment of the invention, when negative material is silicon, tin, aluminium, phosphorus or lithium titanate, negative material is also
Including conductive agent and binder.
In one embodiment of the invention, conductive agent be acetylene black, SPUER P, carbon black, Ketjen black, electrically conductive graphite,
One or more of carbon fiber, carbon nanotube and graphene.
In one embodiment of the invention, binder is Kynoar, polytetrafluoroethylene (PTFE), carboxymethyl cellulose
One or more of sodium, polyolefin, SBR rubber, Viton and Polyurethane.
In one embodiment of the invention, the diaphragm is Nafion membrane, the Nafion membrane of lithiumation or potassium
Nafion membrane.
In one embodiment of the invention, the positive electrode and negative material of the double ion rocking chair type secondary cell
It is carbon materials, diaphragm is Nafion membrane, and electrolyte includes anode electrolyte and electrolyte liquid, and positive and negative electrode passes through diaphragm
It separates, diaphragm both sides are added dropwise respectively in corresponding positive and negative electrode electrolyte.
Second object of the present invention is to provide the preparation method of the double ion rocking chair type secondary cell, including following
Step：
(1) positive electrode, negative material and diaphragm are processed into slabbing；
(2) it is put into diaphragm between the positive electrode and negative material, and described in being added respectively in diaphragm both sides just
Pole electrolyte and electrolyte liquid obtain the double ion rocking chair type secondary cell.
In one embodiment of the invention, further include being coated on aluminium foil or copper after mixing positive electrode and binder
On paillon, the step as anode.
In one embodiment of the invention, further include being coated on aluminium foil or copper after mixing negative material and binder
On paillon, the step of as cathode.
In one embodiment of the invention, positive electrode or negative material are processed into the circle of a diameter of 6-18mm
Piece.
In one embodiment of the invention, a concentration of 0.1-10mol L of positive and negative electrode electrolyte-1.Positive and negative anodes electricity
The volume for solving liquid is 0.01-0.5mL.
The beneficial effects of the present invention are：(1) present invention combination electrolyte double ion rocking chair type secondary cell, for not
It is reacted with positive and negative electrode, has chosen the good ionic liquid of oxidative resistance as anode reaction electrolyte, ensure electrolyte under high pressure
Not oxygenolysis has chosen the ether organic solvent of stabilization of solid dielectric film as negative reaction electrolyte, ensures battery
High coulombic efficiency selects this combination electrolyte that can play the advantage of positive and negative anodes electrolyte simultaneously, ensure that electrolyte shakes
Chair form secondary cell can be in 100mA g-1Under current density, stablize 3000 multi-turns of cycle.
(2) present invention combination electrolyte double ion rocking chair type secondary cell, the up to operating voltage of 4.2V, have up to
99.7% coulombic efficiency can use the positive and negative anodes active material of equivalent, lower the waste of active material, reduce battery at
This.
(3) present invention combination electrolyte double ion rocking chair type secondary cell, cyclical stability, high power library with superelevation
Human relations efficiency and high operating voltage, future have broad application prospects in power battery field.
Description of the drawings
Fig. 1 is the illustraton of model of present invention combination electrolyte double ion rocking chair type secondary cell；
Fig. 2 is the charging and discharging curve of the made combination electrolyte double ion rocking chair type secondary cell of the embodiment of the present invention 1
Figure；
Fig. 3 is the cyclical stability of the made combination electrolyte double ion rocking chair type secondary cell of the embodiment of the present invention 1
Figure；
Fig. 4 is single use 1.5mol L-1The 1- methyl-1s of bis- (fluoroform) sulfimide lithiums-propyl pyrrole alkane is double
The charging and discharging curve figure of the double ion rocking chair type secondary cell of (trifluoro methylsulfonyl) imines salting liquid；
Fig. 5 is single use 1.5mol L-1The 1- methyl-1s of bis- (fluoroform) sulfimide lithiums-propyl pyrrole alkane is double
The cyclical stability figure of the double ion rocking chair type secondary cell of (trifluoro methylsulfonyl) imines salting liquid.
Specific implementation mode
With reference to the accompanying drawings and examples, the specific implementation mode of the present invention is described in further detail.Implement below
Example is not limited to the scope of the present invention for illustrating the present invention.
Embodiment 1：
(1) battery material is prepared according to formula as below：
Positive electrode：Based on mass fraction comprising 90% graphite, 10% Kynoar binder.
Negative material：Based on mass fraction comprising 90% graphite, 10% Kynoar binder.
Battery diaphragm：The Nafion membrane of lithiumation.
Anode electrolyte：1.5mol L-11- methyl-1s-propyl pyrrole alkane bis- (three of bis- (fluoroform) sulfimide lithiums
Fluorine methylsulfonyl) imines salting liquid.
Electrolyte liquid：2.75mol L-1The triethylene glycol dimethyl ether solution of bis- (fluoroform) sulfimide lithiums.
It is coated on copper foil or aluminium foil after positive electrode is mixed with binder respectively, as anode.Above-mentioned electrode is cut
It is cut into the disk of a diameter of 12mm.
It is coated on copper foil or aluminium foil after negative material is mixed with binder respectively, as cathode.Above-mentioned electrode is cut
It is cut into the disk of a diameter of 12mm.
The Nafion membrane of lithiumation is cut into the disk of a diameter of 19mm.
(2) in argon gas glove box assemble CR2032 button cells, battery case related accessory (negative electrode casing, shrapnel, gasket,
Anode cover) it is stainless steel.Above-mentioned battery material is assembled in the following order：Negative electrode casing, gasket, is born shrapnel
Pole sodium piece, diaphragm, anode and anode cover add and the corresponding positive and negative electrode electrolyte of 0.05mL are added dropwise in both sides respectively when diaphragm,
It is pressed on buckle battery mouth sealer and closes electrolyte rocking chair type secondary cell.After battery installs, charge-discharge test is carried out.
Electrochemical property test is carried out to the combination electrolyte double ion rocking chair type secondary cell of above-mentioned making, as a result such as
Fig. 2 and Fig. 3.As can be seen from Figure 2, the average voltage of the battery is up to 4.2V, has higher coulombic efficiency, is filled after 3 circles
Discharge curve shape does not change significantly.The battery has overlength cyclical stability as can be seen from Figure 2, in 50mA g-1Electricity
Under current density, battery can stablize 1200 circle of cycle, in 100mA g-1Under current density, battery can stablize 3000 multi-turns of cycle
Do not decay significantly, and coulombic efficiency is up to 99.7%.These results illustrate the combination electrolyte made by embodiment 1
Double ion rocking chair type secondary cell really has the cyclical stability of high working voltage and overlength.
Embodiment 2：
Anode electrolyte in step (1) is replaced with into 1.5mol L-1Bis- (fluorine sulphonyl) imine lithiums 1- ethyl -3- first
Bis- (fluorine sulphonyl) imide liquors of base imidazoles, negative electrode liquid are 2.75mol L-1Bis- (fluorine sulphonyl) imine lithiums triethylene glycol two
Methyl ether solution.According to the method for step (1)-(2) in embodiment 1, combination electrolyte double ion rocking chair type secondary cell is made.
Embodiment 3：
Anode electrolyte in step (1) is replaced with into 1.5mol L-1Trifluoromethanesulfonic acid lithium N- trimethoxy silicon substrates
Propyl-N, N, N- trimethyl trifluoromethanesulfonic acid solution, negative electrode liquid are 2.75mol L-1Trifluoromethanesulfonic acid lithium three second two
Diethylene glycol dimethyl ether solution.According to the method for step (1)-(2) in embodiment 1, it is secondary to make combination electrolyte double ion rocking chair type
Battery.
Embodiment 4：
Anode electrolyte in step (1) is replaced with into 1.5mol L-1Lithium hexafluoro phosphate N, N- dialkyl pyrrolidiniums
Hexafluorophosphoric acid solution, negative electrode liquid are 2.75mol L-1Lithium hexafluoro phosphate triethylene glycol dimethyl ether solution.According to reality
The method for applying step (1)-(2) in example 1 makes combination electrolyte double ion rocking chair type secondary cell.
Embodiment 5：
Anode electrolyte in step (1) is replaced with into 1.5mol L-1Bis- (fluorine sulphonyl) imines sodium 1- ethyl -3- first
Bis- (fluorine sulphonyl) imide liquors of base imidazoles, negative electrode liquid are 2.75mol L-1Bis- (fluorine sulphonyl) imines sodium triethylene glycol two
The membrane replacement of step (1) is Nafion membrane by methyl ether solution.According to the method for step (1)-(2) in embodiment 1, making group
Close electrolyte double ion rocking chair type secondary cell
Embodiment 6：
Anode electrolyte in step (1) is replaced with into 1.5mol L-1Potassium Hexafluorophosphate N, N- dialkyl pyrrolidiniums
Hexafluorophosphoric acid solution, negative electrode liquid are 2.75mol L-1Potassium Hexafluorophosphate triethylene glycol dimethyl ether solution, by step
(1) membrane replacement is potassium Nafion membrane.According to the method for step (1)-(2) in embodiment 1, it is double to make combination electrolyte
Ion rocking chair type secondary cell.
Embodiment 7：
Anode electrolyte in step (1) is replaced with into 10mol L-1Bis- (fluorine sulphonyl) imine lithiums 1- ethyl -3- first
Bis- (fluorine sulphonyl) imide liquors of base imidazoles, negative electrode liquid are 2.75mol L-1Bis- (fluorine sulphonyl) imine lithiums triethylene glycol two
Methyl ether solution.According to the method for step (1)-(2) in embodiment 1, combination electrolyte double ion rocking chair type secondary cell is made.
Embodiment 8：
Anode electrolyte in step (1) is replaced with into 0.1mol L-1Bis- (fluorine sulphonyl) imine lithiums 1- ethyl -3- first
Bis- (fluorine sulphonyl) imide liquors of base imidazoles, negative electrode liquid are 2.75mol L-1Bis- (fluorine sulphonyl) imine lithiums triethylene glycol two
Methyl ether solution.According to the method for step (1)-(2) in embodiment 1, combination electrolyte double ion rocking chair type secondary cell is made.
Embodiment 9：
Anode electrolyte in step (1) is replaced with into 1.5mol L-1Bis- (fluorine sulphonyl) imine lithiums 1- ethyl -3- first
Bis- (fluorine sulphonyl) imide liquors of base imidazoles, negative electrode liquid are 2.75mol L-1Bis- (fluorine sulphonyl) imine lithiums tetraethylene glycol two
Methyl ether solution.According to the method for step (1)-(2) in embodiment 1, combination electrolyte double ion rocking chair type secondary cell is made.
Embodiment 10：
Anode electrolyte in step (1) is replaced with into 1.5mol L-1Bis- (fluorine sulphonyl) imine lithiums 1- ethyl -3- first
Bis- (fluorine sulphonyl) imide liquors of base imidazoles, negative electrode liquid are 2.75mol L-1Bis- (fluorine sulphonyl) imine lithiums diethylene glycol two
Methyl ether solution.According to the method for step (1)-(2) in embodiment 1, combination electrolyte double ion rocking chair type secondary cell is made.
Embodiment 11：
Anode electrolyte in step (1) is replaced with into 1.5mol L-1Bis- (fluorine sulphonyl) imine lithiums 1- ethyl -3- first
Bis- (fluorine sulphonyl) imide liquors of base imidazoles, negative electrode liquid are 2.75mol L-1Bis- (fluorine sulphonyl) imine lithiums five ethylene glycol two
Methyl ether solution.According to the method for step (1)-(2) in embodiment 1, combination electrolyte double ion rocking chair type secondary cell is made.
Embodiment 12：
Anode electrolyte in step (1) is replaced with into 1.5mol L-1Bis- (fluorine sulphonyl) imine lithiums 1- ethyl -3- first
Bis- (fluorine sulphonyl) imide liquors of base imidazoles, negative electrode liquid are 10mol L-1Bis- (fluorine sulphonyl) imine lithiums triethylene glycol diformazan
Ethereal solution.According to the method for step (1)-(2) in embodiment 1, combination electrolyte double ion rocking chair type secondary cell is made.
Embodiment 13：
Anode electrolyte in step (1) is replaced with into 1.5mol L-1Bis- (fluorine sulphonyl) imine lithiums 1- ethyl -3- first
Bis- (fluorine sulphonyl) imide liquors of base imidazoles, negative electrode liquid are 0.1mol L-1Bis- (fluorine sulphonyl) imine lithiums triethylene glycol two
Methyl ether solution.According to the method for step (1)-(2) in embodiment 1, combination electrolyte double ion rocking chair type secondary cell is made.
Embodiment 14：
Positive electrode in step (1) is replaced with into hard carbon.According to the method for step (1)-(2) in embodiment 1, making group
Close electrolyte double ion rocking chair type secondary cell.
Embodiment 15：
Positive electrode in step (1) is replaced with into soft carbon.According to the method for step (1)-(2) in embodiment 1, making group
Close electrolyte double ion rocking chair type secondary cell.
Embodiment 16：
Positive electrode in step (1) is replaced with into mesoporous carbon.According to the method for step (1)-(2) in embodiment 1, make
Combine electrolyte double ion rocking chair type secondary cell.
Embodiment 17：
Negative material in step (1) is replaced with into hard carbon.According to the method for step (1)-(2) in embodiment 1, making group
Close electrolyte double ion rocking chair type secondary cell.
Embodiment 18：
Negative material in step (1) is replaced with into soft carbon.According to the method for step (1)-(2) in embodiment 1, making group
Close electrolyte double ion rocking chair type secondary cell.
Embodiment 19：
Positive electrode in step (1) is replaced with into mesoporous carbon.According to the method for step (1)-(2) in embodiment 1, make
Combine electrolyte double ion rocking chair type secondary cell.
Embodiment 20：
Negative material in step (1) is replaced with into silicon.According to the method for step (1)-(2) in embodiment 1, combination is made
Electrolyte double ion rocking chair type secondary cell.
Embodiment 21：
Negative material in step (1) is replaced with into tin.According to the method for step (1)-(2) in embodiment 1, combination is made
Electrolyte double ion rocking chair type secondary cell.
Embodiment 22：
Negative material in step (1) is replaced with into aluminium.According to the method for step (1)-(2) in embodiment 1, combination is made
Electrolyte double ion rocking chair type secondary cell.
Embodiment 23：
Negative material in step (1) is replaced with into phosphorus.According to the method for step (1)-(2) in embodiment 1, combination is made
Electrolyte double ion rocking chair type secondary cell.
Embodiment 24：
Negative material in step (1) is replaced with into lithium titanate.According to the method for step (1)-(2) in embodiment 1, make
Combine electrolyte double ion rocking chair type secondary cell.
Comparative example：
Electrolyte liquid in step (1) in embodiment 1 is replaced with into 1.5mol L-1Bis- (fluoroform) sulfimide lithiums
Bis- (trifluoro methylsulfonyl) the imines salting liquids of 1- methyl-1s-propyl pyrrole alkane, with anode electrolyte use identical electrolyte, so
Afterwards according to the method for step (1)-(2) in embodiment 1, double ion rocking chair type secondary cell is made.
Electrochemical property test is carried out to the combination electrolyte double ion rocking chair type secondary cell of above-mentioned making, as a result such as
Fig. 4 and Fig. 5, as shown in Figure 5, the first circle specific capacity in comparative example only have 11mAh/g, and the specific capacity after the circle of circulating battery 20
Already close to 0mAh/g.Mainly since the first circle coulombic efficiency in comparative example only has 20%, lead to its special capacity fade very
Soon.
Embodiment described above is only to absolutely prove preferred embodiment that is of the invention and being lifted, protection model of the invention
It encloses without being limited thereto.Those skilled in the art on the basis of the present invention made by equivalent substitute or transformation, in the present invention
Protection domain within.Protection scope of the present invention is subject to claims.
Claims (10)
1. a kind of double ion rocking chair type secondary cell, including positive electrode, negative material, diaphragm and electrolyte, which is characterized in that
The electrolyte includes anode electrolyte and electrolyte liquid, and the anode electrolyte is the ionic liquid containing alkali metal salt,
The electrolyte liquid is the ether organic solvent containing alkali metal salt identical with anode electrolyte.
2. double ion rocking chair type secondary cell according to claim 1, which is characterized in that in the ionic liquid it is cloudy from
Son is identical as the anion in alkali metal salt.
3. double ion rocking chair type secondary cell according to claim 1, which is characterized in that in the alkali metal salt sun from
Son is selected from Li+、Na+Or K+, the anion in the alkali metal salt is selected from bis- (fluoroform) sulfimide roots, bis- (fluorine sulphonyl)
Imines root, trifluoromethanesulfonic acid root or hexafluoro-phosphate radical.
4. double ion rocking chair type secondary cell according to claim 1, which is characterized in that in the ionic liquid sun from
Son is selected from 1- methyl-1s-propyl pyrrole alkane ion, 1- ethyl-3-methylimidazoles ion, N- trimethoxy silicon substrate propyl-N, N, N-
Trimethyl cation or N, N- dialkyl pyrrolidinium ions.
5. double ion rocking chair type secondary cell according to claim 1, which is characterized in that ether organic solvent is diethyl two
One or more of diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethyleneglycol dimethyl ether and five ethylene glycol dimethyl ether.
6. double ion rocking chair type secondary cell according to claim 1, which is characterized in that the positive electrode is carbon material
Material.
7. double ion rocking chair type secondary cell according to claim 1, which is characterized in that the negative material is carbon material
Material, lithium metal, metallic sodium, metallic potassium, silicon, tin, aluminium, phosphorus or lithium titanate.
8. the double ion rocking chair type secondary cell described according to claim 6 or 7, which is characterized in that the carbon materials are stone
Ink, mesoporous carbon, hard carbon or soft carbon.
9. double ion rocking chair type secondary cell according to claim 1, which is characterized in that the diaphragm be Nafion membrane,
The Nafion membrane of lithiumation or the Nafion membrane of potassium.
10. a kind of preparation method of double ion rocking chair type secondary cell described in claim 1, which is characterized in that including following
Step：
(1) positive electrode, negative material and diaphragm are processed into slabbing；
(2) it is put into diaphragm between the positive electrode and negative material, and the anode electricity is added in diaphragm both sides respectively
Liquid and electrolyte liquid are solved, the double ion rocking chair type secondary cell is obtained.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810556847.6A CN108711636B (en) | 2018-06-01 | 2018-06-01 | Combined electrolyte type dual-ion rocking chair type secondary battery and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810556847.6A CN108711636B (en) | 2018-06-01 | 2018-06-01 | Combined electrolyte type dual-ion rocking chair type secondary battery and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108711636A true CN108711636A (en) | 2018-10-26 |
| CN108711636B CN108711636B (en) | 2020-01-14 |
Family
ID=63871010
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810556847.6A Active CN108711636B (en) | 2018-06-01 | 2018-06-01 | Combined electrolyte type dual-ion rocking chair type secondary battery and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108711636B (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111200158A (en) * | 2018-11-19 | 2020-05-26 | 财团法人工业技术研究院 | Battery with a battery cell |
| CN114188599A (en) * | 2021-12-16 | 2022-03-15 | 华南师大(清远)科技创新研究院有限公司 | High-energy-density dual-electrolyte lithium ion battery and preparation method and application thereof |
| CN116072818A (en) * | 2023-02-17 | 2023-05-05 | 大连理工大学 | Soft carbon material anode of double-ion battery and preparation method thereof |
| WO2023213188A1 (en) * | 2022-05-05 | 2023-11-09 | 珠海冠宇电池股份有限公司 | Electrochemical device |
| JP7422493B2 (en) | 2019-06-04 | 2024-01-26 | 三洋化成工業株式会社 | Lithium ion battery manufacturing method |
| CN114188599B (en) * | 2021-12-16 | 2024-04-19 | 华南师大(清远)科技创新研究院有限公司 | Double-electrolyte lithium ion battery with high energy density and preparation method and application thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060269834A1 (en) * | 2005-05-26 | 2006-11-30 | West William C | High Voltage and High Specific Capacity Dual Intercalating Electrode Li-Ion Batteries |
| WO2010081170A1 (en) * | 2009-01-12 | 2010-07-15 | Rutgers, The State University | Polyhydrogen fluoride based battery |
| CN104600353A (en) * | 2013-11-01 | 2015-05-06 | 微宏动力***（湖州）有限公司 | Anion-cation double intercalated battery |
| CN106674391A (en) * | 2015-11-10 | 2017-05-17 | 华中科技大学 | Iamine-polyanion lithium salt and preparation method thereof as well as application of iamine-polyanion lithium salt as nonaqueous electrolyte |
| CN107069022A (en) * | 2017-03-30 | 2017-08-18 | 华南理工大学 | A kind of chargeable ionic liquid Dual-ion cell and preparation method thereof |
| CN107565167A (en) * | 2016-06-30 | 2018-01-09 | 中国科学院长春应用化学研究所 | A kind of electrolyte and Dual-ion cell |
-
2018
- 2018-06-01 CN CN201810556847.6A patent/CN108711636B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060269834A1 (en) * | 2005-05-26 | 2006-11-30 | West William C | High Voltage and High Specific Capacity Dual Intercalating Electrode Li-Ion Batteries |
| WO2010081170A1 (en) * | 2009-01-12 | 2010-07-15 | Rutgers, The State University | Polyhydrogen fluoride based battery |
| CN104600353A (en) * | 2013-11-01 | 2015-05-06 | 微宏动力***（湖州）有限公司 | Anion-cation double intercalated battery |
| CN106674391A (en) * | 2015-11-10 | 2017-05-17 | 华中科技大学 | Iamine-polyanion lithium salt and preparation method thereof as well as application of iamine-polyanion lithium salt as nonaqueous electrolyte |
| CN107565167A (en) * | 2016-06-30 | 2018-01-09 | 中国科学院长春应用化学研究所 | A kind of electrolyte and Dual-ion cell |
| CN107069022A (en) * | 2017-03-30 | 2017-08-18 | 华南理工大学 | A kind of chargeable ionic liquid Dual-ion cell and preparation method thereof |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111200158A (en) * | 2018-11-19 | 2020-05-26 | 财团法人工业技术研究院 | Battery with a battery cell |
| US11264647B2 (en) | 2018-11-19 | 2022-03-01 | Industrial Technology Research Institute | Battery |
| JP7422493B2 (en) | 2019-06-04 | 2024-01-26 | 三洋化成工業株式会社 | Lithium ion battery manufacturing method |
| CN114188599A (en) * | 2021-12-16 | 2022-03-15 | 华南师大(清远)科技创新研究院有限公司 | High-energy-density dual-electrolyte lithium ion battery and preparation method and application thereof |
| CN114188599B (en) * | 2021-12-16 | 2024-04-19 | 华南师大(清远)科技创新研究院有限公司 | Double-electrolyte lithium ion battery with high energy density and preparation method and application thereof |
| WO2023213188A1 (en) * | 2022-05-05 | 2023-11-09 | 珠海冠宇电池股份有限公司 | Electrochemical device |
| CN116072818A (en) * | 2023-02-17 | 2023-05-05 | 大连理工大学 | Soft carbon material anode of double-ion battery and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108711636B (en) | 2020-01-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107226475B (en) | Potassium ion battery positive electrode material, preparation method thereof and potassium ion battery | |
| CN108963205A (en) | A kind of solid state lithium battery of NEW TYPE OF COMPOSITE anode and its preparation method and application | |
| CN108711636A (en) | A kind of combination electrolyte double ion rocking chair type secondary cell and preparation method thereof | |
| CN109524652A (en) | A kind of covalent organic frame/graphene compositing organic material and preparation method and the application in lithium/anode material of lithium-ion battery | |
| CN106785008A (en) | A kind of graphene-based sodium-ion battery | |
| CN104701541A (en) | Lithium-ion battery with WS2 serving as positive electrode and preparation method of lithium-ion battery | |
| CN110148787A (en) | A kind of electrolyte and lithium-sulfur cell improving lithium-sulfur cell capacity | |
| CN114149319A (en) | Organic sodium supplement additive, positive pole piece and application in sodium ion battery | |
| CN109088101A (en) | A kind of electrolyte and its application | |
| CN108493485A (en) | A kind of preparation method of high power capacity high safety solid state lithium battery | |
| CN109950465A (en) | A kind of method of electrochemical stripping stratified material | |
| CN108550818A (en) | A kind of lithium sulfur battery anode material and its application | |
| CN113299897B (en) | Na (Na) 3 V 2 (PO 4 ) 3 Mixed ion full battery with @ C as positive electrode material | |
| Zhou et al. | Strategies toward anode stabilization in nonaqueous alkali metal–oxygen batteries | |
| WO2020124328A1 (en) | Pre-lithiated negative electrode fabrication method, fabricated pre-lithiated negative electrode, energy storage device, energy storage system, and electrical device | |
| CN107706393B (en) | High-capacity solid lithium ion battery and preparation method thereof | |
| CN107910568B (en) | Lithium primary battery | |
| CN109167104A (en) | A kind of room temperature sodium-sulphur battery and preparation method thereof | |
| CN105514425A (en) | High-performance indoor-temperature sodium ion battery and preparation method thereof | |
| CN109962231A (en) | Metal foil is used as lanthanum ion secondary battery negative pole and lanthanum ion secondary cell and preparation method thereof | |
| CN109950640B (en) | Metal graphite medium-temperature energy storage battery and preparation method thereof | |
| CN109360947B (en) | Preparation method of porous carbon cathode material of quasi-solid-state lithium-sulfur battery | |
| CN110459801A (en) | A kind of sodium base Dual-ion cell and preparation method thereof | |
| CN109378220A (en) | A kind of high voltage mixed type lithium ion super capacitor and preparation method thereof | |
| CN113140791B (en) | Pyrazine electrolyte of lithium-air battery |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |