CN107293733B - Dual-ion battery - Google Patents

Dual-ion battery Download PDF

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CN107293733B
CN107293733B CN201710374794.1A CN201710374794A CN107293733B CN 107293733 B CN107293733 B CN 107293733B CN 201710374794 A CN201710374794 A CN 201710374794A CN 107293733 B CN107293733 B CN 107293733B
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electrolyte
ion battery
battery
negative electrode
positive electrode
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CN107293733A (en
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黄令
武丽娜
沈守宇
许跃峰
孙世刚
李君涛
樊晶晶
周丽丽
沈重亨
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Xiamen University
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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
    • 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
    • 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
    • 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
    • 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
    • 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

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  • Chemical Kinetics & Catalysis (AREA)
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Abstract

The invention provides a double-ion battery, and relates to the technical field of electrochemical energy storage. A dual-ion battery comprises a positive electrode, a negative electrode, a diaphragm and electrolyte, wherein the diaphragm is arranged between the positive electrode and the negative electrode in a spaced mode. The positive electrode includes a graphite-based positive electrode material. The negative electrode material is MnO or metal Sn foil; the electrolyte includes an electrolyte, an organic solvent, and an electrolyte additive. Graphite materials are selected as the anode materials of the battery, and MnO or Sn foils with activity to lithium ions are selected as the cathode materials. The bi-ion battery is obtained by assembly, the raw materials are low in price, the environment is protected, and the rate capability and the coulombic efficiency are good. And the potential of the negative electrode platform is high, the generation of dendritic crystals on the surface of the negative electrode in the repeated charge and discharge process of the battery is inhibited, and the safety of the battery is greatly improved. In addition, the electrolyte additive is added into the electrolyte of the double-ion battery, so that the stability of the battery can be effectively improved, and the rate performance of the battery is improved.

Description

Dual-ion battery
Technical Field
The invention relates to the field of electrochemical energy storage, in particular to a double-ion battery.
Background
Along with the rapid development of the society, the greenhouse effect of air pollution is more and more serious due to the large use of fossil fuels, in addition, along with the wide use of chemical power sources in numerous fields of portable electronic equipment, electric vehicles, medical treatment, military, aerospace science and technology and the like, the chemical power sources are particularly important for researching and developing high-efficiency clean and safe energy storage equipment, and the secondary lithium ion battery is the secondary battery with the most excellent comprehensive performance at present and is also the key energy storage equipment for improving the greenhouse effect due to the outstanding advantages of high energy density, small self-discharge rate, long cycle life, no memory effect, environmental protection and the like.
The working principle of the lithium ion battery is that lithium ions are inserted into and separated from the positive and negative electrode materials in the process of charging the battery, and the lithium ion battery is visually called as a rocking chair type battery, wherein the positive electrode material is the most critical part in the components of the lithium ion battery, and the cost of the positive electrode material accounts for more than half of the whole battery, L iCoO2Although the earliest commercialized lithium ion battery cathode material, cobalt, a raw material, is very expensive and has environmental pollution problems, and is only suitable for small 3C electronic products, and the large-scale use is limited, L nio2、LiMnO2And L ixMn2O4Poor cycle performance of L iFePO4Although having many advantages, there are two fatal disadvantages: low conductivity and low tap density. Therefore, the development of the cathode material is a key for restricting the further improvement of the energy density of the lithium ion battery.
At present, the negative electrode material of the commercial lithium ion battery generally adopts a graphite carbon material, the graphite material has good conductivity, a good layered material is suitable for the insertion/separation of the lithium ion battery, the charging and discharging platform is stable, but the large multiplying power performance of the lithium ion battery is poor.
The double-ion battery is a new design concept, which is based on the simultaneous energy storage of double ions, and the two poles of the battery are subjected to the embedding and removing reactions of two different ions, so that the design overcomes the respective defects of the single-ion battery, and plays a synergistic role. For example, the positive electrode and the negative electrode of the double-graphite battery and the double-graphite battery are made of graphite materials, and the electrolyte anion PF is used in the charging process by utilizing the oxidation-reduction property of the graphite6 -，BF4 -The positive electrode graphite material and the negative electrode graphite material are uniformly embedded with cations, and the electrolyte ions L i are embedded in the positive electrode graphite material and the negative electrode graphite material during discharge+、PF6 -、BF4 -And the double-graphite battery returns to the electrolyte again, so that the double-graphite battery has the advantages of low price, green color, good rate capability and coulombic efficiency and the like.
The inventor finds that the anode material generally has intercalation and deintercalation reaction, alloying and dealloying reaction or conversion reaction in the battery. The existing double-ion battery uses graphite as a negative electrode material, and an embedding/separating reaction occurs in the charging and discharging process, and in addition, the negative electrode of the original double-graphite battery is easy to generate lithium dendrite to cause the problem of potential safety hazard. As the graphite material is used as the anode material, the intercalation potential of anions in the graphite is higher, and the charging voltage reaches 5V, so that the requirement on the electrolyte is high. The electrolyte of the bi-ion battery has the characteristics of wide electrochemical window, good high-voltage stability, and capability of forming a stable SEI film on the surface of a negative electrode material to improve the stability of the battery. In some researches, the ionic liquid is used as the electrolyte, and has the defects of high viscosity, low conductivity, poor wettability on the surface of an electrode, poor rate capability and poor circulation stability, and high price, so that the ionic liquid is difficult to be applied to a practical system as the electrolyte.
Disclosure of Invention
The invention aims to provide a double-ion battery which is high in capacity, good in cycle performance, excellent in rate performance and high in safety performance.
The technical problem to be solved by the invention is realized by adopting the following technical scheme.
The invention provides a dual-ion battery which comprises a positive electrode, a negative electrode, a diaphragm and electrolyte, wherein the diaphragm is arranged between the positive electrode and the negative electrode at intervals. The positive electrode material includes a graphite-based positive electrode material. The negative electrode material is MnO or metal Sn foil; the electrolyte includes an electrolyte, an organic solvent, and an electrolyte additive.
The beneficial effects of the double-ion battery of the embodiment of the invention are as follows:
graphite materials are selected as the anode materials of the battery, and MnO or Sn foils with activity to lithium ions are selected as the cathode materials. The bi-ion battery is obtained by assembly, the raw materials are low in price, the environment is protected, and the rate capability and the coulombic efficiency are good.
MnO or Sn foil with higher platform potential is used as a negative electrode material, and the increase of the platform potential of the negative electrode inhibits dendritic crystals on the surface of the negative electrode in the repeated charge and discharge process of the battery, so that the safety of the battery is greatly improved.
In addition, the electrolyte additive is added into the electrolyte of the double-ion battery, so that the electrochemical window of the electrolyte is wide, the high-voltage stability is good, a stable SEI film can be formed on the surface of a negative electrode material, the stability of the battery is effectively improved, and the rate capability of the battery is improved.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained according to the drawings without inventive efforts.
FIG. 1 is a spherical MnCO of example 1 of the present invention3SEM picture of (1);
FIG. 2 is an SEM image of porous spherical MnO of a micro-nano structure of example 1 of the present invention;
FIG. 3 is a BET characteristic diagram of porous spherical MnO of a micro-nano structure of example 1 of the present invention;
FIG. 4 is a graph showing the variation of discharge capacity of the bi-ion battery prepared in example 1 of the present invention with the volume content of vinylene carbonate;
fig. 5 is a charge-discharge curve diagram of a bi-ion battery of example 1 of the present invention;
fig. 6 is a graph of rate performance of a bi-ion battery of example 1 of the present invention;
fig. 7 is a graph comparing the cycle stability of the dual ion batteries of example 1 of the present invention and comparative example 1;
fig. 8 is a graph comparing the cycle stability of the dual ion batteries of example 1 of the present invention and comparative example 2;
FIG. 9 is a graph showing the variation of discharge capacity of the bi-ion battery according to example 2 of the present invention with the volume content of vinylene carbonate;
fig. 10 is a charge-discharge curve diagram of a bi-ion battery of example 2 of the invention;
fig. 11 is a graph of rate performance for a bi-ion battery of example 2 of the present invention;
fig. 12 is a graph comparing the cycle stability of the dual ion batteries of example 2 of the present invention and comparative example 1.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
The following describes a bi-ion battery according to an embodiment of the present invention.
The invention provides a dual-ion battery, which comprises a positive electrode, a negative electrode, a diaphragm and electrolyte, wherein the diaphragm is arranged between the positive electrode and the negative electrode in a spaced mode. The positive electrode material includes a graphite-based positive electrode material. The negative electrode material is MnO or metal Sn foil; the electrolyte includes an electrolyte, an organic solvent, and an electrolyte additive.
Graphite-based materials are used as a positive electrode material of a battery, and MnO or Sn foil having activity to lithium ions is used as a negative electrode material. The bi-ion battery is obtained by assembly, cobalt materials and the like are not needed, the raw materials are low in price and environment-friendly, and the rate performance and the coulombic efficiency of the prepared battery are good.
Under the condition of larger deviation from equilibrium conditions, the crystal is easy to grow in a dendritic shape to form dendritic crystal, namely dendrite. The dendrite in the negative electrode material can pierce the diaphragm when growing to a certain degree, so that the internal short circuit of the battery is caused, and the personal safety is seriously threatened. According to the embodiment of the invention, MnO or Sn foil with higher platform potential is used as the negative electrode material, the platform potential of the negative electrode is increased, the generation of dendrite on the surface of the negative electrode in the repeated charge and discharge process of the battery is inhibited, and the safety of the battery is greatly improved.
Further, in the preferred embodiment of the present invention, the thickness of the metallic Sn foil is 0.02-2 mm. More preferably, the thickness of the metallic Sn foil is 0.1mm, which can satisfy the matching of battery capacity, reduce polarization, and significantly improve battery capacity and energy density.
Further, in a preferred embodiment of the present invention, the negative electrode material is porous spherical MnO with a micro-nano structure. The porous structure of the lithium ion battery shortens the diffusion path of lithium ions in the charging process of the dual-ion battery, thereby improving the battery cycle stability and rate capability of the dual-ion battery. Meanwhile, the porous material with the micro-nano structure can accelerate the transfer of lithium ions and electrolyte, effectively reduce the expansion of the electrode material and further improve the electrochemical performance of the battery.
Further, the porous spherical MnO of the micro-nano structure is spherical MnCO prepared by a carbonate coprecipitation method3Calcining at 400-550 ℃ for 3-7 hours. Spherical MnCO3MnO is prepared for the raw material, during the preparation process, due to CO2The overflow can form a porous structure inside the fine particles, and a porous structure can be generated among a plurality of fine particles.
The specific surface area of the MnO prepared by the method is measured by an adsorption and desorption method, and the specific surface area of the MnO prepared in the embodiment is 6-7 m by a dynamic nitrogen adsorption pore size distribution test2·g-1The average pore diameter is 15-18 nm, the lower specific surface area of the active material can reduce the contact area of the active material and electrolyte, the occurrence of side reactions is reduced, and the active material is not easy to agglomerate under high current density, so that the cycle performance and the rate capability of the double-ion battery are improved.
In addition, the porous spherical MnO material with the micro-nano structure obtained by the calcination temperature and the calcination time has the advantages of stable structure, environmental friendliness and low discharge platform, and can be applied to energy storage in a large scale.
It is to be understood that, in other embodiments of the present invention, there is no particular limitation on the source of the graphite-based positive electrode material, and commercially available products or self-made graphite-based materials may be used. Commercially available MnO and metallic Sn foils can be used.
Further, in a preferred embodiment of the present invention, the organic solvent includes a chain carbonate. Further preferably, the chain carbonate comprises one or more of ethylene carbonate, ethyl methyl carbonate and diethyl carbonate, more preferably ethyl methyl carbonate. The chain carbonate is used as an organic solvent of the electrolyte, has oxidation resistance, can remarkably improve the oxidation resistance of the electrolyte, has low viscosity, and can increase the solubility of the electrolyte. And the methyl ethyl carbonate is used as the electrolyte, the electrochemical window is wide, the methyl ethyl carbonate is not easily decomposed at higher voltage, the stability is good, and the conductivity of the electrolyte and the multiplying power and energy density characteristics of the dual-ion battery are obviously improved, so that the capacity and the cycle performance of the dual-ion battery are effectively improved.
Further, in a preferred embodiment of the present invention, the electrolyte additive includes one or more of vinylene carbonate, fluoroethylene carbonate and succinic anhydride. More preferably vinylene carbonate, which is a novel organic film-forming additive and overcharge protection additive for lithium ion batteries, has good high and low temperature performance and anti-ballooning function, and can improve the capacity and cycle life of the batteries.
Further, in a preferred embodiment of the present invention, the volume percentage of the electrolyte additive in the electrolyte, i.e., in the mixed solvent of the electrolyte additive and the organic solvent, is 1% to 20%, more preferably 1% to 10%, still more preferably 2% to 5%, still more preferably 3%. The electrolyte additive such as vinylene carbonate and the like is used as a film forming additive, the content of the electrolyte additive influences the amount of a passive film on the surface of a negative electrode of the battery, and further influences the conductivity and the capacity of the battery, and the stability and the capacity of the battery can be effectively improved by selecting the electrolyte additive with the content of 1-5%.
Further, in the preferred embodiment of the present invention, the electrolyte is selected from one or more of lithium hexafluorophosphate, lithium tetrafluoroborate, potassium hexafluorophosphate and sodium hexafluorophosphate. Lithium hexafluorophosphate is preferred. Lithium hexafluorophosphate has high solubility, high dissociation degree and small anion radius in the organic solvent, and increases the capacity of the anion intercalated graphite.
Furthermore, in the preferred embodiment of the invention, the molar concentration of the electrolyte in the organic solvent is 0.4 mol/L-saturated concentration, more preferably 0.4 mol/L-4 mol/L, and more preferably 2 mol/L. compared with the prior art in which the electrolyte is 0.1-0.2 mol/L, the embodiment of the invention adopts the high-concentration electrolyte, increases the number of conductive ions, and effectively improves the capacity and rate capability of the battery.
Further, in the preferred embodiment of the present invention, the following steps are employed to obtain the bi-ion battery. The electrolyte is configured in a glove box, and a graphite positive electrode, a graphite negative electrode MnO or metal Sn foil, the electrolyte and a diaphragm are assembled into the double-ion battery. The voltage of the double-ion battery is preferably 1.0V-5.5V; the current density of the bi-ion battery is preferably 50mA/g to 600 mA/g.
The features and properties of the present invention are described in further detail below with reference to examples.
Example 1
The present embodiment provides a dual-ion battery:
preparing 2 mol/L electrolyte containing lithium hexafluorophosphate in a glove box, wherein the electrolyte is a mixed solvent of methyl ethyl carbonate, ethylene carbonate and vinylene carbonate, the volume fraction of the vinylene carbonate in the mixed solvent is 5%, standing the prepared electrolyte in the glove box, and manufacturing a bi-ion battery in the glove box, wherein the positive electrode is commercial graphite, the negative electrode is porous spherical MnO with a micro-nano structure, and the diaphragm is a commercially available diaphragm.
The porous spherical MnO with the micro-nano structure is spherical MnCO prepared by a carbonate coprecipitation method3Calcining at 470 deg.C for 5.5 h.
Example 2
The present embodiment provides a dual-ion battery:
preparing 2 mol/L electrolyte containing lithium hexafluorophosphate in a glove box, wherein the electrolyte is a mixed solvent of methyl ethyl carbonate, ethylene carbonate and vinylene carbonate, the volume fraction of the vinylene carbonate in the mixed solvent is 5%, standing the prepared electrolyte in the glove box, and manufacturing the bi-ion battery in the glove box, wherein the positive electrode is commercial graphite, the negative electrode is a metal Sn foil with the thickness of 0.1mm, and the diaphragm is a commercial diaphragm.
Example 3
Preparing 0.4 mol/L electrolyte containing lithium tetrafluoroborate in a glove box, wherein the electrolyte is a mixed solvent of methyl ethyl carbonate and fluoroethylene carbonate, the volume fraction of the fluoroethylene carbonate in the mixed solvent is 10%, standing the prepared electrolyte in the glove box, and manufacturing a bi-ion battery in the glove box, wherein the positive electrode is multilayer graphite oxide, the negative electrode is porous spherical MnO with a micro-nano structure, and the diaphragm is a commercially available diaphragm.
The porous spherical MnO with the micro-nano structure is spherical MnCO prepared by a carbonate coprecipitation method3Calcining at 400 ℃ for 7 h.
Example 4
Preparing 4 mol/L electrolyte containing sodium hexafluorophosphate in a glove box, wherein the electrolyte is a mixed solvent of ethyl methyl carbonate, diethyl carbonate and succinic anhydride, the volume fraction of the succinic anhydride in the mixed solvent is 20%, standing the prepared electrolyte in the glove box, and manufacturing the bi-ion battery in the glove box, wherein the positive electrode is multilayer graphite oxide, the negative electrode is a metal Sn foil with the thickness of 0.02mm, and the diaphragm is a commercially available diaphragm.
Example 5
And preparing saturated-concentration electrolyte containing potassium hexafluorophosphate in a glove box, wherein the electrolyte is a mixed solvent of ethyl methyl carbonate, vinylene carbonate and fluoroethylene carbonate, and the volume fraction of the vinylene carbonate and the fluoroethylene carbonate in the mixed solvent is 1%. Standing the prepared electrolyte in a glove box; and manufacturing the double-ion battery in a glove box, wherein the anode is multilayer graphite oxide, the cathode is porous spherical MnO with a micro-nano structure, and the diaphragm is a commercially available diaphragm.
The porous spherical MnO with the micro-nano structure is spherical MnCO prepared by a carbonate coprecipitation method3Calcining at 550 deg.C for 3 hr.
Example 6
The present embodiment provides a dual-ion battery:
preparing 2 mol/L electrolyte containing lithium hexafluorophosphate in a glove box, wherein the electrolyte is a mixed solvent of ethyl methyl carbonate, ethylene carbonate and vinylene carbonate, the volume fraction of the vinylene carbonate in the mixed solvent is 2%, standing the prepared electrolyte in the glove box, and manufacturing the bi-ion battery in the glove box, wherein the positive electrode is graphite, the negative electrode is metal Sn foil with the thickness of 2mm, and the diaphragm is a commercially available diaphragm.
Example 7
The present embodiment provides a dual-ion battery:
preparing 2 mol/L electrolyte containing lithium hexafluorophosphate in a glove box, wherein the electrolyte is a mixed solvent of methyl ethyl carbonate, ethylene carbonate and vinylene carbonate, the volume fraction of the vinylene carbonate in the mixed solvent is 3%, standing the prepared electrolyte in the glove box, and manufacturing a bi-ion battery in the glove box, wherein the positive electrode is graphite, the negative electrode is porous spherical MnO with a micro-nano structure, and the diaphragm is a commercially available diaphragm.
Comparative example 1
This comparative example provides a bi-ion battery:
preparing 2 mol/L electrolyte containing lithium hexafluorophosphate in a glove box, wherein the electrolyte is a mixed solvent of ethyl methyl carbonate, ethylene carbonate and vinylene carbonate, the volume fraction of the vinylene carbonate in the mixed solvent is 5%, standing the prepared electrolyte in the glove box, and manufacturing the bi-ion battery in the glove box, wherein the positive electrode is a graphite electrode, the negative electrode is a lithium sheet, and the diaphragm is a commercially available diaphragm.
Comparative example 2
This comparative example provides a bi-ion battery:
preparing 2 mol/L electrolyte containing lithium hexafluorophosphate in a glove box, wherein the electrolyte is a mixed solvent of ethyl methyl carbonate, ethylene carbonate and vinylene carbonate, the volume fraction of the vinylene carbonate in the mixed solvent is 5%, standing the prepared electrolyte in the glove box, and manufacturing the bi-ion battery in the glove box, wherein the positive electrode is a graphite electrode, the negative electrode is a MnO material obtained by combining a hydrothermal method and calcination, and the diaphragm is a commercially available diaphragm.
Test example 1
Determination of spherical MnCO according to the invention, example 13And a porous spherical MnO of a micro-nano structure, wherein SEM images of the porous spherical MnO of the micro-nano structure and the porous spherical MnO of the micro-nano structure are respectively shown in figures 1 and 2, and a BET characteristic diagram of the porous spherical MnO of the micro-nano structure is shown in figure 3.
As can be seen from FIG. 1, the produced MnCO3The spherical shape is presented; as can be seen from fig. 2, the sintered MnO is in a porous spherical shape with a micro-nano structure; as can be seen from FIG. 3, the specific surface area of the porous spherical MnO having the micro-nano structure was 6.7m2·g-1The average pore diameter was 17.6 nm.
Test example 2
The discharge capacity of the bi-ion battery was determined for vinylene carbonate at different volume fractions by varying the volume fraction of vinylene carbonate using the method provided in example 1. Wherein the current density of the double-ion battery charging and discharging test is 400mA/g, and the voltage range is 1.5V-5V. The test results are shown in fig. 4.
As can be seen from FIG. 4, the discharge specific capacity of the dual-ion battery provided by the invention reaches 10 mAh/g-110 mAh/g in an electrolyte system. Along with the increase of the content of the vinylene carbonate (electrolyte additive), the discharge specific capacity of the bi-ion battery is remarkably improved, and when the volume fraction of the vinylene carbonate reaches 2% -5%, the discharge specific capacity of the bi-ion battery reaches the highest.
Test example 3
The double-ion batteries provided by the embodiment 1, the comparative example 1 and the comparative example 2 are subjected to charge and discharge tests, the current density is 400mA/g, and the voltage range is 1.5V-5V. The test results are shown in FIGS. 5 to 8.
As can be seen from fig. 5, after the bi-ion battery provided in this embodiment is stabilized, the reversible charge-discharge capacity and the coulombic efficiency of the bi-ion battery substantially reach those reported in the prior art. As can be seen from fig. 6, the capacity of the dual-ion battery provided in this embodiment does not significantly decrease at a high rate, and the coulombic efficiency also reaches 95% or more, which is 3% higher than that of the conventional literature at a 5C rate. As can be seen from fig. 7, the dual-ion battery provided by the present embodiment has good cycle performance, and the capacity retention rate after 200 cycles is 98%, which is 10% higher than that of the literature. As can be seen from fig. 8, the capacity of the bi-ion battery assembled by using MnO prepared by a co-precipitation method in combination with a calcination method as a negative electrode and graphite is high by 50%, and the stability is significantly improved.
Test example 4
The discharge capacity of the bi-ion battery was determined for vinylene carbonate at different volume fractions by varying the volume fraction of vinylene carbonate using the method provided in example 2. Wherein the current density of the double-ion battery charging and discharging test is 400mA/g, and the voltage range is 3V-5V. The test results are shown in fig. 9.
As can be seen from fig. 9, the capacity of the dual-ion battery provided in this embodiment reaches 10mAh/g to 110mAh/g in the electrolyte system. Along with the increase of the content of the vinylene carbonate (electrolyte additive), the discharge specific capacity of the bi-ion battery is remarkably improved, and when the volume fraction of the vinylene carbonate reaches 20-50%, the discharge specific capacity and the coulombic efficiency of the bi-ion battery are both high.
Test example 5
The double-ion batteries provided by the embodiment 2 and the comparative example 1 of the invention are subjected to charge and discharge tests, the current density is 400mA/g, and the voltage range is 3V-5V. The test results are shown in FIGS. 10 to 12.
As can be seen from fig. 10, the reversible charge-discharge capacity and the coulombic efficiency of the bi-ion battery provided in this embodiment after stabilization substantially reach those of the bi-ion battery reported in the prior art. As can be seen from fig. 11, the coulombic efficiency of the dual-ion battery provided in this embodiment can also be maintained at 98% under a large rate, which substantially reaches the coulombic efficiency reported in the existing literature, and when the rate returns to a small rate of 0.5C, the coulombic efficiency is higher than the coulombic efficiency reported in the existing literature by about 10%. As can be seen from fig. 12, the dual-ion battery provided in this embodiment has good cycle performance, and the capacity retention rate after 150 cycles substantially reaches the capacity retention rate reported in the existing literature.
In summary, the graphite material of the dual-ion battery in the embodiment of the invention is used as the positive electrode material, MnO or Sn foil with a higher plateau potential is used as the negative electrode material, and the dual-ion battery is assembled, wherein the increase of the plateau potential of the negative electrode inhibits dendritic crystals on the surface of the negative electrode in the repeated charging and discharging process of the battery, the safety of the battery is greatly improved, MnO is a porous sphere with a micro-nano structure, the contact area of an active material and an electrolyte can be reduced due to the lower specific surface area of MnO, side reactions can be reduced, and the MnO is not easy to agglomerate under high current density, and a shorter ion transmission path is provided for L i + and the like in the charging process of the dual-ion battery due to the existence of the porous structure, so that the capacity, the cycle performance and the rate performance of the battery are improved.
The embodiments described above are some, but not all embodiments of the invention. The detailed description of the embodiments of the present invention is not intended to limit the scope of the invention as claimed, but is merely representative of selected embodiments of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

Claims (6)

1. A dual-ion battery comprises a positive electrode, a negative electrode, a diaphragm and electrolyte, wherein the diaphragm and the electrolyte are arranged between the positive electrode and the negative electrode at intervals, and the dual-ion battery is characterized in that the positive electrode comprises a graphite positive electrode material, and the negative electrode material is porous spherical MnO with a micro-nano structure; the specific surface area of the porous spherical MnO ranges from 6 m to 7m2·g-1The average pore diameter is 15-18 nm; the electrolyte comprises an electrolyte, an organic solvent and an electrolyte additive; the electrolyte is selected from one or more of lithium hexafluorophosphate, lithium tetrafluoroborate, potassium hexafluorophosphate and sodium hexafluorophosphate; the organic solvent is a mixture of ethylene carbonate and methyl ethyl carbonate; the electrolyte additive is selected from one or more of vinylene carbonate, fluoroethylene carbonate and succinic anhydride.
2. The bi-ion battery of claim 1, wherein the porous spherical MnO is a spherical MnCO prepared by a carbonate co-precipitation method3Calcining at 400-550 ℃ for 3-7 hours.
3. The bi-ion battery of claim 1, wherein the electrolyte additive is present in the electrolyte at a volume percentage of 1% to 20%.
4. The bi-ion battery of claim 1, wherein the molar concentration of the electrolyte in the organic solvent is between 0.4 mol/L and a saturation concentration.
5. The bi-ion battery according to any one of claims 1 to 4, wherein the voltage of the bi-ion battery is 1.0V to 5.5V.
6. The bi-ion battery of any one of claims 1-4, wherein the current density of the bi-ion battery is 50 mA/g-600 mA/g.
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