CN107293733A - A kind of Dual-ion cell - Google Patents
A kind of Dual-ion cell Download PDFInfo
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- CN107293733A CN107293733A CN201710374794.1A CN201710374794A CN107293733A CN 107293733 A CN107293733 A CN 107293733A CN 201710374794 A CN201710374794 A CN 201710374794A CN 107293733 A CN107293733 A CN 107293733A
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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
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
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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
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
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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
- H01M10/056—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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/387—Tin or alloys based on tin
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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
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
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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 provides a kind of Dual-ion cell, is related to electrochemical energy storage technical field.A kind of Dual-ion cell, including positive pole, negative pole, the barrier film and electrolyte that are interval between positive pole and negative pole.Positive pole including graphite-like positive electrode.Negative material is MnO or metal Sn paper tinsels；Electrolyte includes electrolyte, organic solvent and electrolysis additive.From positive electrode of the graphite type material as battery, negative material is used as from MnO the or Sn paper tinsel active to lithium ion.Assembling obtains Dual-ion cell, and low in raw material price, environmental protection, high rate performance and coulombic efficiency are good.And negative pole plateau potential is high, it is suppressed that the generation of battery negative terminal surface dendrite during repeated charge, the security of battery is greatly improved.In addition, with the addition of electrolysis additive in the electrolyte of Dual-ion cell, the stability of battery can be effectively improved, improves the high rate performance of battery.
Description
Technical field
The present invention relates to electrochemical energy storage field, and more particularly to a kind of Dual-ion cell.
Background technology
With the fast development of society, a large amount of of fossil fuel use, and cause air pollution greenhouse effect increasingly severe, this
Outside, the widely using in various fields such as mancarried electronic aid, electric car, medical treatment, military and space science and technology with electrochmical power source,
It is particularly important for the energy storage device of research and development high-efficiency cleaning, safety, secondary lithium battery is because its energy density is high, oneself
The outstanding advantages such as discharge rate is small, have extended cycle life, memory-less effect and environmental protection, are current combination properties the most excellent two
Primary cell, is also to improve the crucial energy storage device of greenhouse effects.
Lithium ion battery is as representative secondary cell, and it refers to using Lithium-ion embeding compound as positive and negative electrode
The general name of the battery of material.Its operation principle be in battery charging process, lithium ion come and gone between positive and negative pole material it is embedded-
Abjection, is visually referred to as " rocking chair type battery ".Positive electrode be lithium ion battery composition part in most critical part, its into
Originally more than half of whole battery is accounted for.LiCoO2Although as realizing commercialized anode material for lithium-ion batteries earliest,
The price of raw material cobalt is sufficiently expensive, and there is problem of environmental pollution, and is only applicable to small-sized 3C electronic products, makes on a large scale
With being restricted.And LiNiO2、LiMnO2And LixMn2O4Cycle performance it is poor, LiFePO4Although there are many advantages, exist
Two fatal shortcomings：Low electrical conductivity and low tap density.Therefore, the development of positive electrode is restriction lithium ion battery energy
The key that metric density is further lifted.
Lithium ion battery is to use metal Li as negative material earliest, but in long-term charge and discharge process, lithium metal
The easy efflorescence in surface and generation dendrite, cause the capacity attenuation and safety problem of lithium anode, so limiting actual secondary
It is used widely in lithium battery.At present, commercial Li-ion battery negative material typically uses graphite-like carbon material, graphite material
Expect good conductivity, good stratified material is adapted to the intercalation/deintercalation of lithium ion battery, and charge and discharge platform is stable, but its big multiplying power
Poor performance.
Dual-ion cell is a kind of new design concept proposed, and it is the energy storage based on double ion simultaneously, in electricity
It is the embedded abjection reaction of two kinds of different ions on the two poles of the earth in pond, this design overcomes the respective shortcoming of single ion battery, sent out
Synergy is waved.Such as double graphite cells, the positive pole of double graphite cells and negative pole are graphite material, using graphite certainly
Electrolytic anion PF in the oxidation-reduction quality of body, charging process6 -, BF4 -Deng in embedded positive pole graphite material, cation insertion
In negative pole graphite material；Electrolyte ion Li in discharge process+、PF6 -、BF4 -Deng returning to again among electrolyte, this pair of stone
The advantages of black battery shows cheap, green, high rate performance and good coulombic efficiency.
Inventor it has been investigated that, general anode material occurs embedded abjection reaction, alloying and removes alloy in the battery
Reaction or conversion reaction.Existing Dual-ion cell graphite is intercalation/deintercalation in charge and discharge process as negative material
Reaction, in addition, original pair of graphite cell negative pole is also easy to produce Li dendrite and causes security hidden trouble, the present invention is selected and preparation pair
The active material of lithium ion, its voltage platform is slightly above graphite type material, can lift the security of battery.Due to graphite material
Material is as positive electrode, and insertion current potential of the anion in graphite is higher, and charging voltage reaches 5V, and this is just wanted to electrolyte
Ask very high.It is that electrochemical window is wide, high voltage stability is good that the electrolyte of Dual-ion cell, which has the special feature that, in negative material
Surface forms stable SEI films, increases the stability of battery.Research ionic liquid in part is as electrolyte, and its viscosity is big, electricity
Conductance is low, poor in electrode surface wellability, therefore high rate performance and cyclical stability are poor, while its is expensive, therefore, with from
Sub- liquid is difficult to be applied in practical systems as electrolyte.
The content of the invention
It is an object of the invention to provide a kind of Dual-ion cell, this Dual-ion cell capacity height, good cycle, multiplying power
Excellent performance, and security performance is high.
The present invention is solved its technical problem and realized using following technical scheme.
The present invention proposes a kind of Dual-ion cell, including positive pole, negative pole, the barrier film and the electricity that are interval between positive pole and negative pole
Solve liquid.Positive electrode includes graphite-like positive electrode.Negative material is MnO or metal Sn paper tinsels；Electrolyte includes electrolyte, organic
Solvent and electrolysis additive.
The beneficial effect of the Dual-ion cell of the embodiment of the present invention is：
From positive electrode of the graphite type material as battery, from MnO the or Sn paper tinsel conduct active to lithium ion
Negative material.Assembling obtains Dual-ion cell, and low in raw material price, environmental protection, high rate performance and coulombic efficiency are good.
Using MnO the or Sn paper tinsels with compared with high platform current potential as negative material, the increase of negative pole plateau potential, it is suppressed that battery
The generation of negative terminal surface dendrite during repeated charge, the security of battery is greatly improved.
In addition, with the addition of electrolysis additive in the electrolyte of Dual-ion cell, not only cause the electrochemistry of electrolyte
Window is wide, high voltage stability is good, additionally it is possible to one layer of stable SEI film is formd on negative material surface, battery is effectively improved
Stability, improve battery high rate performance.
Brief description of the drawings
In order to illustrate the technical solution of the embodiments of the present invention more clearly, below will be attached to what is used required in embodiment
Figure is briefly described, it will be appreciated that the following drawings illustrate only certain embodiments of the present invention, therefore is not construed as pair
The restriction of scope, for those of ordinary skill in the art, on the premise of not paying creative work, can also be according to this
A little accompanying drawings obtain other related accompanying drawings.
Fig. 1 is 1 spherical MnCO of the embodiment of the present invention3SEM figure；
Fig. 2 schemes for the porous spherical MnO of the micro-nano structure of the embodiment of the present invention 1 SEM；
Fig. 3 is the porous spherical MnO of the micro-nano structure of the embodiment of the present invention 1 BET phenograms；
Fig. 4 is the Dual-ion cell discharge capacity of the preparation of the embodiment of the present invention 1 with the change of vinylene carbonate volume content
Change curve map；
Fig. 5 is the charging and discharging curve figure of the Dual-ion cell of the embodiment of the present invention 1；
Fig. 6 is the high rate performance figure of the Dual-ion cell of the embodiment of the present invention 1；
Fig. 7 is that the cyclical stability of the Dual-ion cell of the embodiment of the present invention 1 and comparative example 1 compares figure；
Fig. 8 is that the cyclical stability of the Dual-ion cell of the embodiment of the present invention 1 and comparative example 2 compares figure；
Fig. 9 is bent with the change of vinylene carbonate volume content for the Dual-ion cell discharge capacity of the embodiment of the present invention 2
Line chart；
Figure 10 is the charging and discharging curve figure of the Dual-ion cell of the embodiment of the present invention 2；
Figure 11 is the high rate performance figure of the Dual-ion cell of the embodiment of the present invention 2；
Figure 12 is that the cyclical stability of the Dual-ion cell of the embodiment of the present invention 2 and comparative example 1 compares figure.
Embodiment
, below will be in the embodiment of the present invention to make the purpose, technical scheme and advantage of the embodiment of the present invention clearer
Technical scheme be clearly and completely described.Unreceipted actual conditions person, builds according to normal condition or manufacturer in embodiment
The condition of view is carried out.Agents useful for same or the unreceipted production firm person of instrument, are the conventional production that can be obtained by commercially available purchase
Product.
The Dual-ion cell of the embodiment of the present invention is specifically described below.
A kind of Dual-ion cell provided in an embodiment of the present invention, including positive pole, negative pole, be interval between positive pole and negative pole
Barrier film and electrolyte.Positive electrode includes graphite-like positive electrode.Negative material is MnO or metal Sn paper tinsels；Electrolyte includes electricity
Xie Zhi, organic solvent and electrolysis additive.
Using graphite type material as the positive electrode of battery, negative pole is used as using MnO the or Sn paper tinsel active to lithium ion
Material.Assembling obtains Dual-ion cell, without using cobalt material etc., low in raw material price, environmental protection, obtained battery multiplying power
Performance and coulombic efficiency are good.
Crystal is in the case where deviation equilibrium condition is larger, and easily the growth of branches and tendrils shape, forms skeleton, i.e. dendrite.
Dendritic growth in negative material will puncture barrier film to a certain extent, cause internal short-circuit of battery, seriously threaten personal safety.
The embodiment of the present invention is using MnO the or Sn paper tinsels with compared with high platform current potential as negative material, the increase of negative pole plateau potential, it is suppressed that
The generation of battery negative terminal surface dendrite during repeated charge, the security of battery is greatly improved.
Further, in present pre-ferred embodiments, metal Sn paper tinsels thickness is 0.02-2mm.It is highly preferred that metal Sn
The thickness of paper tinsel is 0.1mm, and the thickness can meet the matching of battery capacity, reduce polarization, significantly improve battery capacity and energy
Density.
Further, in present pre-ferred embodiments, negative material is the porous spherical MnO of micro-nano structure.Its is porous
Structure causes the diffusion path that lithium ion is shortened in Dual-ion cell charging process, so that the battery for improving Dual-ion cell is followed
Ring stability and high rate performance.Meanwhile, the porous material of micro-nano structure can accelerate the transmission of lithium ion and electrolyte, effectively
The expansion of electrode material is reduced, the chemical property of battery is further improved.
Further, the porous spherical MnO of micro-nano structure is the spherical MnCO prepared by carbonate co-precipitation3
Calcine 3-7 hours and be made under the conditions of 400-550 DEG C.Spherical MnCO3MnO is prepared for raw material, in preparation process, due to CO2Overflow
Go out, can produce multi-pore structure between multiple particulates in interparticle formation loose structure.
The specific surface area of MnO made from the above method is determined by adsorption desorption method, and passes through dynamic N2 adsorption pore-size distribution
Test obtains MnO specific surface areas manufactured in the present embodiment for 6~7m2·g-2, average pore size is 15~18nm, its relatively low ratio table
Area can make active material reduce the contact area with electrolyte, reduce the generation of side reaction, and be difficult at higher current densities
Reunite, so as to improve the cycle performance and high rate performance of Dual-ion cell.
In addition, the porous spherical MnO material structures of the micro-nano structure obtained by above-mentioned calcining heat and calcination time are steady
Fixed, environment-friendly, discharge platform is low, can large-scale application energy storage.
It is understood that in other embodiments of the invention, graphite-like positive electrode source is not particularly limited,
Commercially available prod or homemade graphite type material can be used.Commercially available prod can also be selected to MnO, metal Sn paper tinsels.
Further, in present pre-ferred embodiments, organic solvent includes linear carbonate.It is further preferred that chain
Shape carbonic ester includes the one or more in ethylene carbonate, methyl ethyl carbonate and diethyl carbonate, more preferably methyl ethyl carbonate
Ester.Using linear carbonate as the organic solvent of electrolyte, it has inoxidizability, can significantly improve the anti-oxidant of electrolyte
Ability, and linear carbonate viscosity is low, by increasing capacitance it is possible to increase the solubility of electrolyte.And methyl ethyl carbonate is used for electrolyte, its electricity
Chemical window is wide, be difficult to be decomposed under high voltage, stability is good, significantly improves the electrical conductivity and Dual-ion cell of electrolyte
Multiplying power, energy density characteristics, therefore, effectively improve the capacity and cycle performance of Dual-ion cell.
Further, in present pre-ferred embodiments, electrolysis additive includes vinylene carbonate, fluoro ethylene
One or more in alkene ester and succinic anhydride.More preferably vinylene carbonate, vinylene carbonate is a kind of lithium-ion electric
The new organic film for additive in pond and additives for overcharge protection additive, can be with good high temperature performance and anti-inflatable function
Improve the capacity and cycle life of battery.
Further, in present pre-ferred embodiments, in the electrolytic solution, i.e., in electrolysis additive and organic solvent
In the mixed solvent, the percent by volume of electrolysis additive is 1%~20%, more preferably 1%~10%, more preferably
2%~5%, more preferably 3%.The electrolysis additives such as vinylene carbonate are used as a kind of film for additive, its content
The amount of GND surface passivated membrane is influenceed, and then influences the electrical conductivity and capacity of battery, the electrolysis of 1%~5% content is selected
Solution additive, can be effectively increased the stability and capacity of battery.
Further, in present pre-ferred embodiments, electrolyte selects lithium hexafluoro phosphate, LiBF4, hexafluoro phosphorus
One or more in sour potassium and sodium hexafluoro phosphate.Preferably lithium hexafluoro phosphate.Lithium hexafluoro phosphate is molten in above-mentioned organic solvent
Solution degree is high, degree of dissociation is high, anion radius is small, adds the capacity that anion inserts embedding graphite.
Further, in present pre-ferred embodiments, the molar concentration of electrolyte in organic solvent is 0.4mol/L
~saturated concentration, more preferably 0.4mol/L~4mol/L, more preferably 2mol/L.Compared to electrolyte in the prior art
For 0.1~0.2mol/L, the embodiment of the present invention uses the electrolyte of high concentration, adds conductive ion number, effectively improve battery
Capacity and high rate performance.
Further, in present pre-ferred embodiments, adopt to be prepared by the following steps and obtain Dual-ion cell.In glove box
The middle above-mentioned electrolyte of configuration, Dual-ion cell is assembled into by graphite-like positive pole, negative pole MnO or metal Sn paper tinsels and electrolyte, barrier film.
The voltage of Dual-ion cell is preferably 1.0V~5.5V；The current density of Dual-ion cell is preferably 50mA/g~600mA/g.
The feature and performance to the present invention are described in further detail with reference to embodiments.
Embodiment 1
A kind of Dual-ion cell that the present embodiment is provided：
Electrolyte of the 2mol/L containing lithium hexafluoro phosphate is configured in glove box, wherein, electrolyte is methyl ethyl carbonate, carbonic acid
The mixed solvent of ethyl and vinylene carbonate, vinylene carbonate is 5% in the volume fraction of in the mixed solvent.Will be above-mentioned
The electrolyte configured is statically placed in glove box；Dual-ion cell is made in glove box, wherein, just extremely commercial graphite, negative pole
For the porous spherical MnO of micro-nano structure, barrier film is commercially available barrier film.
The porous spherical MnO of above-mentioned micro-nano structure is the spherical MnCO prepared by carbonate co-precipitation3470
5.5h is calcined under the conditions of DEG C to be made.
Embodiment 2
A kind of Dual-ion cell that the present embodiment is provided：
Electrolyte of the 2mol/L containing lithium hexafluoro phosphate is configured in glove box, wherein, electrolyte is methyl ethyl carbonate, carbonic acid
The mixed solvent of ethyl and vinylene carbonate, vinylene carbonate is 5% in the volume fraction of in the mixed solvent.Will be above-mentioned
The electrolyte configured is statically placed in glove box；Dual-ion cell is made in glove box, wherein, just extremely commercial graphite, negative pole
The metal Sn paper tinsels for being 0.1mm for thickness, barrier film is commercially available barrier film.
Embodiment 3
In glove box configure electrolyte of the 0.4mol/L containing LiBF4, wherein, electrolyte be methyl ethyl carbonate and
The mixed solvent of fluorinated ethylene carbonate, fluorinated ethylene carbonate is 10% in the volume fraction of in the mixed solvent.Match somebody with somebody above-mentioned
The electrolyte put is statically placed in glove box；Dual-ion cell is made in glove box, wherein, just extremely multilayer oxygen graphite is born
The extremely porous spherical MnO of micro-nano structure, barrier film is commercially available barrier film.
The porous spherical MnO of above-mentioned micro-nano structure is the spherical MnCO prepared by carbonate co-precipitation3400
7h is calcined under the conditions of DEG C to be made.
Embodiment 4
Electrolyte of the 4mol/L containing sodium hexafluoro phosphate is configured in glove box, wherein, electrolyte is methyl ethyl carbonate, carbonic acid
The mixed solvent of diethylester and succinic anhydride, succinic anhydride is 20% in the volume fraction of in the mixed solvent.By above-mentioned configuration well
Electrolyte be statically placed in glove box；Dual-ion cell is made in glove box, wherein, just extremely multilayer oxygen graphite, negative pole is
Thickness is 0.02mm metal Sn paper tinsels, and barrier film is commercially available barrier film.
Embodiment 5
In glove box configure saturated concentration the electrolyte containing Potassium Hexafluorophosphate, wherein, electrolyte be methyl ethyl carbonate,
The mixed solvent of vinylene carbonate, fluorinated ethylene carbonate, vinylene carbonate and fluorinated ethylene carbonate are in mixed solvent
In volume fraction be 1%.The good electrolyte of above-mentioned configuration is statically placed in glove box；Dual-ion cell is made in glove box,
Wherein, just extremely multilayer oxygen graphite, negative pole is the porous spherical MnO of micro-nano structure, and barrier film is commercially available barrier film.
The porous spherical MnO of above-mentioned micro-nano structure is the spherical MnCO prepared by carbonate co-precipitation3550
3h is calcined under the conditions of DEG C to be made.
Embodiment 6
A kind of Dual-ion cell that the present embodiment is provided：
Electrolyte of the 2mol/L containing lithium hexafluoro phosphate is configured in glove box, wherein, electrolyte is methyl ethyl carbonate, carbonic acid
The mixed solvent of ethyl and vinylene carbonate, vinylene carbonate is 2% in the volume fraction of in the mixed solvent.Will be above-mentioned
The electrolyte configured is statically placed in glove box；Dual-ion cell is made in glove box, wherein, just extremely graphite, negative pole is thickness
The metal Sn paper tinsels for 2mm are spent, barrier film is commercially available barrier film.
Embodiment 7
A kind of Dual-ion cell that the present embodiment is provided：
Electrolyte of the 2mol/L containing lithium hexafluoro phosphate is configured in glove box, wherein, electrolyte is methyl ethyl carbonate, carbonic acid
The mixed solvent of ethyl and vinylene carbonate, vinylene carbonate is 3% in the volume fraction of in the mixed solvent.Will be above-mentioned
The electrolyte configured is statically placed in glove box；Dual-ion cell is made in glove box, wherein, just extremely graphite, negative pole is micro-
The porous spherical MnO of micro-nano structure, barrier film is commercially available barrier film.
Comparative example 1
A kind of Dual-ion cell that this comparative example is provided：
Electrolyte of the 2mol/L containing lithium hexafluoro phosphate is configured in glove box, wherein, electrolyte is methyl ethyl carbonate, carbonic acid
The mixed solvent of ethyl and vinylene carbonate, vinylene carbonate is 5% in the volume fraction of in the mixed solvent.Will be above-mentioned
The electrolyte configured is statically placed in glove box；Dual-ion cell is made in glove box, wherein, just extremely graphite-like electrode is born
Extremely lithium piece, barrier film is commercially available barrier film.
Comparative example 2
A kind of Dual-ion cell that this comparative example is provided：
Electrolyte of the 2mol/L containing lithium hexafluoro phosphate is configured in glove box, wherein, electrolyte is methyl ethyl carbonate, carbonic acid
The mixed solvent of ethyl and vinylene carbonate, vinylene carbonate is 5% in the volume fraction of in the mixed solvent.Will be above-mentioned
The electrolyte configured is statically placed in glove box；Dual-ion cell is made in glove box, wherein, just extremely graphite-like electrode is born
The MnO materials extremely obtained with hydro-thermal method with reference to calcining, barrier film is commercially available barrier film.
Test example 1
Determine the spherical MnCO that the embodiment of the present invention 1 is provided3With the porous spherical MnO of micro-nano structure, the SEM figures point of the two
Not as depicted in figs. 1 and 2, and the porous spherical MnO of micro-nano structure BET phenograms it is as shown in Figure 3.
As shown in Figure 1, prepared MnCO3Present spherical；As shown in Figure 2, micro-nano structure is presented in the MnO of sintering out
Porous spherical；From the figure 3, it may be seen that the porous spherical MnO of micro-nano structure, its specific surface area is 6.7m2·g-2, average pore size is
17.6nm。
Test example 2
The method provided using embodiment 1, changes the volume fraction of vinylene carbonate, determines the carbon of different volumes fraction
The discharge capacity of the Dual-ion cell of sour vinylene.The wherein current density 400mA/g of Dual-ion cell charge-discharge test, electricity
Press scope:1.5V~5V.Test result is as shown in Figure 4.
As shown in Figure 4, the specific discharge capacity for the Dual-ion cell that the present invention is provided reaches 10mAh/g in electrolyte system
~110mAh/g.With the increase of vinylene carbonate (electrolysis additive) content, putting for Dual-ion cell is significantly improved
Electric specific capacity, and when vinylene carbonate volume fraction reaches 2%~5%, the specific discharge capacity of Dual-ion cell reaches most
It is high.
Test example 3
Charge-discharge test is carried out to the Dual-ion cell that the embodiment of the present invention 1, comparative example 1 and comparative example 2 are provided, electric current is close
Spend 400mA/g, voltage range:1.5V~5V.Test result is shown in Fig. 5~8.
Knowable to Fig. 5, the reversible capability of charging and discharging and coulombic efficiency of the Dual-ion cell that the present embodiment is provided after stabilization
Basically reach the reversible capacity and coulombic efficiency of the Dual-ion cell of existing literature report.It will be appreciated from fig. 6 that what the present embodiment was provided
Dual-ion cell capacity under big multiplying power is not substantially decayed, and coulombic efficiency also reaches more than 95%, compared with existing literature, 5C
Under multiplying power, capacity wants high by 3%.As shown in Figure 7, the Dual-ion cell good cycle that the present embodiment is provided, after circulating 200 times
Capability retention is 98%, and 10% is higher by compared with the literature.As shown in Figure 8, the MnO prepared with coprecipitation combination calcination method is done
Negative pole and the capacity that graphite is assembled into Dual-ion cell are high by 50%, and stability is significantly improved.
Test example 4
The method provided using embodiment 2, changes the volume fraction of vinylene carbonate, determines the carbon of different volumes fraction
The discharge capacity of the Dual-ion cell of sour vinylene.The wherein current density 400mA/g of Dual-ion cell charge-discharge test, electricity
Press scope:3V~5V.Test result is as shown in Figure 9.
As shown in Figure 9, the capacity for the Dual-ion cell that the present embodiment is provided reaches 10mAh/g in the electrolyte system
~110mAh/g.With the increase of vinylene carbonate (electrolysis additive) content, putting for Dual-ion cell is significantly improved
Electric specific capacity, and when vinylene carbonate volume fraction reaches 20%~50%, the specific discharge capacity of Dual-ion cell and storehouse
Human relations efficiency is higher.
Test example 5
Charge-discharge test, current density 400mA/ are carried out to the Dual-ion cell that the embodiment of the present invention 2, comparative example 1 are provided
G, voltage range:3V~5V.Test result is shown in Figure 10~12.
As shown in Figure 10, the present embodiment is provided Dual-ion cell reversible capability of charging and discharging after stabilization and coulomb effect
Rate basically reaches the reversible capacity and coulombic efficiency of the Dual-ion cell of existing literature report.As shown in Figure 11, the present embodiment is carried
The Dual-ion cell of confession coulombic efficiency under big multiplying power can also keep 98%, basically reach the coulombic efficiency of existing literature report,
When returning again to small multiplying power 0.5C, coulombic efficiency is higher by 10% or so than the coulombic efficiency that existing literature is reported.As shown in Figure 12, originally
The Dual-ion cell good cycle that embodiment is provided, capability retention basically reaches existing literature report after circulating 150 times
Capability retention.
In summary, the Dual-ion cell graphite type material of the embodiment of the present invention is as positive electrode, from higher
MnO the or Sn paper tinsels of plateau potential assemble a kind of Dual-ion cell as negative material.The increase of negative pole plateau potential, it is suppressed that
The generation of battery negative terminal surface dendrite during repeated charge, the security of battery is greatly improved.MnO is micro-nano structure
Porous spherical, its relatively low specific surface area can make active material reduce the contact area with electrolyte, reduce the generation of side reaction,
And be difficult to reunite at higher current densities, the presence of its loose structure is carried to Li+ in Dual-ion cell charging process etc. insertion
For shorter ion transmission path, so as to improve the capacity of this battery, cycle performance and high rate performance.Electrolyte in electrolyte
Concentration is higher, adds conductive ion number, and battery capacity and high rate performance are greatly improved.And electrolyte is with the addition of in the electrolytic solution
Additive, one layer of stable SEI film is formd on negative material surface, the stability of battery is effectively improved.
Embodiments described above is a part of embodiment of the invention, rather than whole embodiments.The reality of the present invention
The detailed description for applying example is not intended to limit the scope of claimed invention, but is merely representative of the selected implementation of the present invention
Example.Based on the embodiment in the present invention, what those of ordinary skill in the art were obtained under the premise of creative work is not made
Every other embodiment, belongs to the scope of protection of the invention.
Claims (10)
1. a kind of Dual-ion cell, including positive pole, negative pole, the barrier film that is interval between the positive pole and the negative pole and electrolysis
Liquid, it is characterised in that the positive pole includes graphite-like positive electrode, and the negative material of the negative pole is MnO or metal Sn paper tinsels；Institute
Stating electrolyte includes electrolyte, organic solvent and electrolysis additive.
2. Dual-ion cell according to claim 1, it is characterised in that the negative material is the porous ball of micro-nano structure
Shape MnO.
3. Dual-ion cell according to claim 2, it is characterised in that the porous spherical MnO is coprecipitated by carbonate
The spherical MnCO that shallow lake method is prepared3Calcine 3-7 hours and be made under the conditions of 400-550 DEG C.
4. Dual-ion cell according to claim 1, it is characterised in that the organic solvent is selected from ethylene carbonate, carbon
One or more in sour methyl ethyl ester and diethyl carbonate.
5. Dual-ion cell according to claim 1, it is characterised in that the electrolysis additive is selected from vinylene carbonate
One or more in ester, fluorinated ethylene carbonate and succinic anhydride.
6. Dual-ion cell according to claim 1, it is characterised in that in the electrolyte, the electrolyte addition
The percent by volume of agent is 1%~20%.
7. Dual-ion cell according to claim 1, it is characterised in that the electrolyte is selected from lithium hexafluoro phosphate, tetrafluoro
One or more in lithium borate, Potassium Hexafluorophosphate and sodium hexafluoro phosphate.
8. Dual-ion cell according to claim 7, it is characterised in that the electrolyte rubbing in the organic solvent
Your concentration is 0.4mol/L~saturated concentration.
9. the Dual-ion cell according to claim 1~8 any one, it is characterised in that the electricity of the Dual-ion cell
Press as 1.0V~5.5V.
10. the Dual-ion cell according to claim 1~8 any one, it is characterised in that the electricity of the Dual-ion cell
Current density is 50mA/g~600mA/g.
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