CN108933234A - Electrode material, electrode slice, electrolyte and lithium ion secondary battery - Google Patents
Electrode material, electrode slice, electrolyte and lithium ion secondary battery Download PDFInfo
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- CN108933234A CN108933234A CN201710365804.5A CN201710365804A CN108933234A CN 108933234 A CN108933234 A CN 108933234A CN 201710365804 A CN201710365804 A CN 201710365804A CN 108933234 A CN108933234 A CN 108933234A
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- additive
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- electrode 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/364—Composites as mixtures
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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
- 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
- H01M10/0567—Liquid materials characterised by the additives
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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
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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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
- H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
-
- 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
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0025—Organic electrolyte
-
- 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
A kind of lithium ion secondary battery, the lithium ion secondary battery include an electrode film, a negative electrode plate, an isolation film and an electrolyte；It include additive at least one of the electrode film, the negative electrode plate and the electrolyte, which is Prussian blue analogue compound；When containing the additive in the electrode film, additive mass percent shared in the electrode film is 0.5%~5%；When containing the additive in the negative electrode plate, additive mass percent shared in the negative electrode plate is 0.5%~5%；When containing the additive in the electrolyte, additive mass percent shared in the electrolyte is 0.5%~5%.The invention further relates to a kind of electrode material, a kind of electrode slice and a kind of electrolyte.
Description
Technical field
The present invention relates to field of lithium ion battery more particularly to a kind of electrode material for lithium ion cell, electrode slice, electrolysis
Liquid and lithium ion secondary battery.
Background technique
Lithium ion battery is the green high-capacity environment-protecting battery occurred the 1990s, since it is with voltage height, volume
Small, light weight, specific energy height, memory-less effect, the advantages that pollution-free, self discharge is small, the service life is long, mobile phone, laptop,
Video camera, digital camera, tablet computer etc. emphasize light and short, multi-functional portable electronic product using upper rapid proliferation.
In recent years, with the failure of the Global Oil energy and the development of new energy technology, applied on automobile power
Lithium ion battery technology rapidly develops.Thus, to the performance of lithium ion secondary battery, more stringent requirements are proposed.
Work long hours to meet electric car, high course continuation mileage, can in high and low temperature environment normal use, can quickly fill
Electricity and the requirement with the long life need lithium ion secondary battery to have higher discharge-rate, energy density and follow
The ring service life.
Summary of the invention
In view of this, the present invention provides a kind of high-discharge-rate, high-energy density and the lithium ion secondary in high circulation service life
Electrode material for battery, electrode slice, electrolyte and lithium ion secondary battery.
A kind of electrode material is used for lithium ion secondary battery；The electrode material includes an additive, which is that class is general
Shandong scholar's indigo plant compound, in the electrode material, mass percent shared by the additive is 0.5%~5%.
Further, the molecular formula of such Prussian is：AxMy(FeCN6).nH2O, wherein A is alkali metal
Element, M are transition metal element, wherein 0 < x < 2, y=1+ (1-x)/3.
Further, such Prussian exists with crystal form.
Further, the crystal grain diameter of such Prussian is 100nm~1000nm.
Further, which is the one of which of positive electrode material and negative electrode material.
A kind of electrode slice is used for lithium ion secondary battery；The electrode slice is including a conductive current collector and is coated in the conduction
Source/drain on collector；It is characterized in that, the source/drain contains electrode material described above.
A kind of electrolyte is used for lithium ion secondary battery；The electrolyte further includes an additive, which is the general Shandong of class
Scholar's indigo plant compound, in the electrolyte, mass percent shared by the additive is 0.5%~5%.
Further, the molecular formula of such Prussian is：AxMy(FeCN6).nH2O, wherein A is alkali metal
Element, M are transition metal element, 0 < x < 2, y=1+ (1-x)/3.
Further, the crystal grain diameter of such Prussian is 100nm~1000nm.
A kind of lithium ion secondary battery, the lithium ion secondary battery include an electrode film, a negative electrode plate, an isolation film
An and electrolyte；It include additive at least one of the electrode film, the negative electrode plate and the electrolyte, the additive
For Prussian blue analogue compound；When containing the additive in the electrode film, the additive is shared in the electrode film
Mass percent be 0.5%~5%；When containing the additive in the negative electrode plate, the additive is in the negative electrode
Shared mass percent is 0.5%~5% in piece；When containing the additive in the electrolyte, the additive is at this
Shared mass percent is 0.5%~5% in electrolyte.
Compared with prior art, the embodiment of the present invention is in electrode slice at least the one of electrode material, electrode slice and electrolyte
It can effectively improve lithium ion secondary using the characteristic of Prussian blue analogue compound added with Prussian blue analogue compound in a
Discharge-rate, energy density and the cycle life of battery.
Detailed description of the invention
Fig. 1 is the structural schematic diagram of lithium ion secondary battery of the present invention.
Fig. 2 is the crystal structure figure of Prussian blue analogue compound provided by the invention.
Fig. 3 is the energy density test result figure of the lithium ion secondary battery of embodiment provided by the invention and comparative example.
Fig. 4 is the discharge-rate test result figure of the lithium ion secondary battery of embodiment provided by the invention and comparative example.
Fig. 5 be embodiment provided by the invention and comparative example lithium in the charge-discharge magnification of 0.7C/0.7C and at room temperature from
The test result figure of the cycle life of sub- secondary cell.
Main element symbol description
| Lithium ion secondary battery | 100 |
| Electrode film | 1 |
| Negative electrode plate | 2 |
| Isolation film | 3 |
| Electrolyte | 4 |
| Shell | 5 |
Specific embodiment
For can the present invention is further explained reaches the technical means and efficacy that predetermined goal of the invention taken, below in conjunction with compared with
Good embodiment, to electrode for lithium ion secondary battery material provided by the invention, electrode slice, electrolyte and lithium ion secondary electricity
Specific embodiment, structure, feature and its effect in pond are made as described in detail below.
Referring to Fig. 1, present pre-ferred embodiments provide a kind of lithium ion secondary battery 100, the lithium ion secondary battery
100 include an electrode film 1, a negative electrode plate 2, an isolation film 3, an electrolyte 4 and a shell 5.The electrode film 1, this is negative
Electrode slice 2, the isolation film 3 and the electrolyte 4 are housed in the shell 5.The isolation film 3 is set to the electrode film 1 and should
Between negative electrode plate 2.The electrolyte 4 is filled in the shell 5.
The electrode film 1 includes that a conductive current collector (not shown) and one are living coated in the positive electrode in the conductive current collector
Property layer (not shown).
It wherein, include positive electrode material in the positive electrode active layer.
In the present embodiment, which includes a positive electrode active materials, a conductive agent, a binder and an addition
Agent.
Wherein, in the positive electrode, mass percent shared by the additive is 0.5%~5%.
In the present embodiment, which includes that a conductive current collector (not shown) and one are coated in the conduction afflux
Negative electrode active layer (not shown) on body.
It wherein, include negative electrode material in the negative electrode active layer.The negative electrode material include a negative electrode active material,
One conductive agent and a binder.
Specifically, in the electrode film, which can be electrolytic aluminum foil.Preferably, the conductive current collector
For 10-20 microns of electrolytic aluminum foil of thickness.
Specifically, in the negative electrode plate, which can be electrolytic copper foil.Preferably, the conductive current collector
For 7-15 microns of electrolytic copper foil of thickness.
Wherein, the positive electrode active materials are the transition metal oxide of lithium.The transition metal oxide of the lithium is
LiCoO2、LiMn2O4、LiMnO2、Li2MnO4、LiFePO4、Li1+aMn1-xMxO2、LiCo1-xMxO2、LiFe1-xMxPO4、LiMn2- yMyO4、Li2Mn1-xO4, wherein M be selected from one of Ni, Co, Mn, Al, Cr, Mg, Zr, Mo, V, Ti, B, F and Y or a variety of,
0 < x < 1,0 < y < 1,0≤a < 0.2.
The negative electrode active material is in natural graphite, artificial graphite, soft carbon, hard carbon, lithium titanate, silicon and silicon-carbon alloy
One or two kinds of arbitrary proportions mixture.
Wherein, which can be at least one of carbon black conductive agent, graphite agent, graphene conductive agent etc..
Specifically, which can be selected from acetylene black, Super P, Super S, 350G, carbon fiber (VGCF), carbon
Nanotube (CNTs) and Ketjen black (KetjenblackEC300J, KetjenblackEC600JD, Carbon ECP, Carbon
At least one of ECP600JD) etc..
Specifically, which can be selected from KS-6, KS-15, SFG-6, SFG-15 (chemical industry standard model) etc..
Wherein, the binder can in fluorinated resin, polyolefin compound and cellulose compound at least
It is a kind of.
Wherein, which is Prussian blue analogue compound.
Specifically, the molecular formula of such Prussian is：AxMy(FeCN6).nH2O, wherein A is alkali metal member
Element, M are transition metal element.Preferably, A is K or Na, M Fe.Wherein, 0 < x < 2, y=1+ (1-x)/3.
Wherein, such Prussian exists with crystal form, and crystal structure is as shown in Figure 2.
Further, such Prussian is time micron grade crystal.Wherein, secondary micron grade refers to than micron
Grade small but that nanometer is not achieved.
Specifically, the range for defining time micron is 100nm~1000nm.
In the present embodiment, the crystal grain diameter of such Prussian is about 100nm.
Wherein, which is to have microcellular structure, can allow lithium ion or alkali metal ion pass freely through and electronics cannot
By macromolecule membrane.Specifically, the material of the isolation film is with polypropylene (Polypropylene, PP), polyethylene
Based on (polyethylene, PE), it is placed between the positive/negative plate of inside battery.The main function of the isolation film is：Isolation is just
Negative electrode tab prevents inside battery anode and cathode short-circuit, ion can be made to pass through, and has the function of keeping electrolyte.
Wherein, in the present embodiment, which includes non-aqueous organic solvent and the lithium that is dissolved in non-aqueous organic solvent
Salt.
Further, the non-aqueous organic solvent includes cyclic carbonate and/or linear carbonate.
Wherein, the cyclic carbonate be one or both of ethylene carbonate, propene carbonate or gamma-butyrolacton with
Upper arbitrary proportion mixing.
Wherein, the linear carbonate is selected from dimethyl carbonate, butylene, diethyl carbonate, dipropyl carbonic acid
Ester, methyl ethyl carbonate, methyl propyl carbonate, ethyl propyl carbonic acid ester, methyl formate, Ethyl formate, propyl formate, methyl acetate, acetic acid
The mixing of one or more of ethyl ester, propyl acetate, methyl propionate, ethyl propionate or propyl propionate arbitrary proportion.Into one
Step ground, the lithium salts are Li (FSO2)2N、LiPF6、LiBF4、LiBOB、LiODFB、LiAsF6、Li(CF3SO2)2N、LiCF3SO3、
LiClO4One or more of arbitrary proportion mixing.
In other embodiments, it is also possible in the only negative electrode material include the additive, at this point, the additive
Shared mass percent is 0.5%~5% in the negative electrode material.
In other embodiments, it is also possible to only include the additive in the electrolyte, at this point, the additive exists
Shared mass percent is 0.5%~5% in the electrolyte.
In other embodiments, at least two in the positive electrode material, the negative electrode material, the electrolyte be can also be
It include the additive in kind, and when containing the additive in the electrode film, additive institute in the electrode film
The mass percent accounted for is 0.5%~5%；When containing the additive in the negative electrode plate, the additive is in the negative electricity
Shared mass percent is 0.5%~5% in pole piece；When containing the additive in the electrolyte, which exists
Shared mass percent is 0.5%~5% in the electrolyte.
The reaction principle of such Prussian is as follows：
When charging,
Positive reaction equation is：
AxMn y[FeII(CN)6]-e-→Ax-1Mn y[FeIII(CN)6]+A+；
Negative reaction formula is：
Ax-1Mn y[FeIII(CN)6]+e-+A+→AxMn y[FeII(CN)6]；
When electric discharge,
Positive reaction equation is：
Ax-1Mn y[FeIII(CN)6]+e-+A+→AxMn y[FeII(CN)6]；
Negative reaction formula is：
AxMn y[FeII(CN)6]-e-→Ax-1Mn y[FeIII(CN)6]+A+。
The present invention is specifically described below by Examples and Comparative Examples.
Embodiment
By mass percent be 95~98% positive electrode active materials, mass percent be 0.5~3% conductive agent, matter
The additive that the binder and mass percent that amount percentage is 0.5~2% are 0.5%~5% makes to form the positive electrode
Piece.
Comparative example
By mass percent be 95~98% positive electrode active materials, mass percent be 0.5~3% conductive agent and matter
The binder that amount percentage is 0.5~2% makes to form an electrode film.
The electrode film being made using above-described embodiment and comparative example makes a lithium ion secondary battery respectively, to this
Lithium ion secondary battery carries out the detection of energy density, discharge-rate and cycle life respectively, and testing result please refers to respectively
Fig. 3-5.
From the figure 3, it may be seen that including that the mean energy density ratio of the lithium ion secondary battery (embodiment) of additive does not contain
The mean energy density of the lithium ion secondary battery (comparative example) of additive improves 3%.
As shown in Figure 4, include additive lithium ion secondary battery (embodiment) 2C discharge-rate than not containing adding
Add the 2C discharge-rate more 15% of the lithium ion secondary battery (comparative example) of agent.
As shown in Figure 5, include additive lithium ion secondary battery (embodiment) cycle life than not containing addition
The cycle life of the lithium ion secondary battery (comparative example) of agent promotes 50% or more.
The present invention the positive electrode material, the negative electrode material, the electrolyte at least one in be added to it is a small amount of (shared
Mass percent be 0.5%~5%) Prussian blue analogue compound, 1) cell potential change situation under, such general Shandong
The transition metal valence state of scholar's indigo plant compound changes (redox reaction), and its alkali metal ion can be as in lithium ion battery
Lithium ion it is the same the deintercalation and insertion of alkali metal ion occurs in the positive and negative end migration, so can normally operate
Relatively large number of capacitance is obtained under current potential, to increase the energy density of the lithium ion secondary battery；2) due to class Prussia
The content of blue compound is less, does not influence the original operating potential of lithium ion battery；3) crystalline substance of such Prussian
After the deintercalation of the alkali metal ion of body, the original position of alkali metal ion is vacant, so as to form the channel passed through for lithium ion,
These channels can provide better ionic conductivity to the lithium ion of lithium battery interior, to promote lithium ion secondary battery
Discharge-rate；4) substance in the electrolyte can carry out micro reaction in the active material surface of positive and negative electrode piece, if
The positive and negative electrode piece surface modification or absorption other materials (Prussian blue analogue in such as this case), can reduce the electrolyte and this just
The collision probability on negative electrode plate surface, to reduce the chance that the electrolyte carries out irreversible reaction, to improve lithium ion secondary
The cycle life of battery；5) all positive-active materials on the market are adapted to using Prussian blue analogue compound as additive
Material, negative electrode active material and electrolyte, importing are easier.
The above is only better embodiment of the invention, not the limitation to the present invention in any form, though
The right present invention has been that better embodiment is disclosed above, is not intended to limit the invention, any person skilled in the art,
Without departing from the scope of the present invention, when the technology contents using the disclosure above are modified or are modified to
With the equivalent implementations of variation, but without departing from the technical solutions of the present invention, according to the technical essence of the invention to
Any simple modification, equivalent change and modification that upper embodiment is done, all of which are still within the scope of the technical scheme of the invention.
Claims (10)
1. a kind of electrode material is used for lithium ion secondary battery；It is characterized in that, the electrode material includes an additive, this adds
Adding agent is Prussian blue analogue compound, and in the electrode material, mass percent shared by the additive is 0.5%~5%.
2. electrode material as described in claim 1, which is characterized in that the molecular formula of such Prussian is：AxMy
(FeCN6).nH2O, wherein A is alkali metal element, and M is transition metal element, wherein 0 < x < 2, y=1+ (1-x)/3.
3. electrode material as described in claim 1, which is characterized in that such Prussian exists with crystal form.
4. electrode material as claimed in claim 3, which is characterized in that the crystal grain diameter of such Prussian is
100nm~1000nm.
5. electrode material as described in claim 1, which is characterized in that the electrode material is positive electrode material and negative electrode material
One of which.
6. a kind of electrode slice is used for lithium ion secondary battery；The electrode slice includes a conductive current collector and collects coated in the conduction
Source/drain on fluid；It is characterized in that, the source/drain contains described in any one of the claims 1-5
Electrode material.
7. a kind of electrolyte is used for lithium ion secondary battery；It is characterized in that, the electrolyte further includes an additive, the addition
Agent is Prussian blue analogue compound, and in the electrolyte, mass percent shared by the additive is 0.5%~5%.
8. electrolyte as claimed in claim 7, which is characterized in that the molecular formula of such Prussian is：AxMy
(FeCN6).nH2O, wherein A is alkali metal ion, and M is transition metal element, 0 < x < 2, y=1+ (1-x)/3.
9. electrolyte as claimed in claim 7, which is characterized in that the crystal grain diameter of such Prussian is
100nm~1000nm.
10. a kind of lithium ion secondary battery, which includes an electrode film, a negative electrode plate, an isolation film
An and electrolyte；It is characterized in that, including addition at least one of the electrode film, the negative electrode plate and the electrolyte
Agent, the additive are Prussian blue analogue compound；When containing the additive in the electrode film, the additive is in the positive electricity
Shared mass percent is 0.5%~5% in pole piece；When containing the additive in the negative electrode plate, the additive
Shared mass percent is 0.5%~5% in the negative electrode plate；It, should when containing the additive in the electrolyte
Additive mass percent shared in the electrolyte is 0.5%~5%.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114784239A (en) * | 2022-04-08 | 2022-07-22 | 深圳华钠新材有限责任公司 | Mixed positive electrode material, electrode and electrical device |
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