WO2016110127A1 - Matériau actif d'électrode négative pour une batterie au lithium-ion/sodium-ion, électrode négative et batterie - Google Patents

Matériau actif d'électrode négative pour une batterie au lithium-ion/sodium-ion, électrode négative et batterie Download PDF

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WO2016110127A1
WO2016110127A1 PCT/CN2015/089690 CN2015089690W WO2016110127A1 WO 2016110127 A1 WO2016110127 A1 WO 2016110127A1 CN 2015089690 W CN2015089690 W CN 2015089690W WO 2016110127 A1 WO2016110127 A1 WO 2016110127A1
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compound
negative electrode
active material
composite
gep
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李会巧
李文武
翟天佑
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华中科技大学
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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
    • 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
    • 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
    • H01M10/054—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
    • 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
    • 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
    • H01M4/5805—Phosphides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • 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

Definitions

  • the invention belongs to the field of electrochemistry and battery technology, and more particularly relates to a negative electrode active material for a lithium ion/sodium ion battery, a negative electrode and a battery.
  • Lithium-ion batteries have higher voltage, higher capacity, and lower weight than batteries such as nickel-metal hydride and nickel-cadmium. Therefore, in recent years, lithium secondary batteries have been widely used as main power sources for mobile communication instruments, portable electronic instruments, electric bicycles, electric two-wheel vehicles, electric vehicles, and the like.
  • lithium secondary batteries have been widely used as main power sources for mobile communication instruments, portable electronic instruments, electric bicycles, electric two-wheel vehicles, electric vehicles, and the like.
  • Searching for new energy storage systems to overcome traditional fuel energy storage systems has become a challenge.
  • Rechargeable lithium batteries have many advantages such as low price, long cycle life, high energy density and excellent reversibility.
  • rechargeable lithium ion batteries often use graphite as a negative electrode material, but the commercial graphite negative electrode material used in rechargeable lithium batteries has a capacity of only 372 mA h/g, and the lithium ion has a low embedding potential in graphite, which is easy.
  • the transition metal oxide can also be used as the negative electrode material of the battery, and its specific capacity can reach a high level, about 700-1500 mA h/g, but its first coulombic efficiency is relatively low, generally below 60%, and it is not suitable for commercial lithium battery anode. material.
  • the present invention provides a negative electrode active material for a lithium ion/sodium ion secondary battery, a negative electrode, and a battery, and aims to provide a high specific capacity, a first coulomb efficiency, and a charge.
  • the discharge voltage platform has small difference and moderate voltage platform, and is suitable for the negative electrode of lithium ion battery and sodium ion battery, and provides a lithium ion battery and a sodium ion battery including the negative electrode, thereby solving the current lithium ion battery and sodium ion battery.
  • the negative electrode has insufficient capacity or the first coulombic efficiency is low.
  • anode active material for a lithium ion/sodium ion battery comprising:
  • a phosphonium compound and/or a first complex formed by the phosphonium compound and elemental P and/or elemental Ge; and/or a second complex formed by the phosphonium compound and a conductive component,
  • the conductive component itself has electrical conductivity; and/or a third composite formed by the first composite and the conductive component, wherein the phosphonium compound comprises one or more of the following:
  • (iii) a multi-component phosphonium compound formed by P and Ge and an element M, and M is one or more selected from the group consisting of Li, Si, Sn, Pb, Zn, Mn, Fe, Co and Cu.
  • the first composite may be an excess of Ge or/and P coated on the surface of the phosphonium compound, or a phosphonium compound coated on an excess of Ge or/and P surface; or a phosphonium compound and an excess of Ge
  • the solid solution formed by or/and P may also be doped with elemental Ge or/and P into the phosphonium compound.
  • Excessive Ge and P may be crystalline or amorphous, and phosphonium compounds may It is crystalline or amorphous.
  • the second/triple composite is different from the general physical mixing, but a composite obtained by high-energy mechanical ball milling or the like, in which the active material is uniformly and fully compounded with the conductive component and has a strong interaction or even a bond.
  • the composite has stable material structure, small particle size and large specific surface area, which is beneficial to the infiltration and penetration of the electrolyte, and facilitates the transport of lithium ions/sodium ions and electrons, and the conductive component can also buffer the active component in the charge. Volume expansion during discharge. Since the second/third composite contains a relatively high conductive component, the conductive component or the conductive agent may not be added when the electrode film is formed, and the second/third composite may be directly mixed with the binder and then coated. On the current collector.
  • the phosphonium compound and the first/second/three complex are used as the anode material of the lithium/sodium ion battery, they may be coated or directly grown on a two-dimensional conductive substrate such as a copper foil, or may be coated or directly grown in three places.
  • a two-dimensional conductive substrate such as a copper foil
  • the conductive substrate such as foamed nickel, carbon cloth/carbon paper or other three-dimensional conductive substrate which can be used as a current collector, it can also be mixed with carbon nanotubes, nano metal, graphene, etc., and then filtered to form a self-supporting structure.
  • the integrated electrode is used directly as a negative electrode for lithium/sodium ion batteries.
  • the binary composition compound formed by P and Ge includes GeP, GeP 2 , GeP 3 , GeP 4 , GeP 5 , Ge 2 P 2 , Ge 3 P, Ge 2 P 3 , and Ge 3 P One or several of 4 .
  • binary non-ratio compound formed by P and Ge comprises one or more of the following:
  • the binary non-ratio compound formed by P and Ge comprises one or more of the following:
  • the binary non-ratio compound formed by P and Ge includes one or more of the following:
  • the binary non-ratio compound formed by P and Ge also includes one of a solid solution formed of a compound of P and Ge and an excess of elemental P and/or Ge. A variety.
  • the conductive component has a mass of 10% to 70% of the total mass of the second/triple composite. In a still further preferred embodiment, wherein the conductive component has a mass of 20% to 60% of the total mass of the second/triple composite.
  • the quality of the conductive component accounts for 10% to 70% of the total mass of the second/triple composite
  • the performance of the battery is better when the second/third composite is used as the negative electrode of the secondary battery.
  • a phosphonium compound When a phosphonium compound is used as a negative electrode active material, lithium ions or sodium ions are embedded in the electrode, causing the volume of the negative electrode to expand, thereby greatly attenuating the electrochemical performance.
  • the addition of conductive components has two functions, on one hand, it can improve the transfer of electrons; on the other hand, it can also buffer the volume expansion to optimize the electrode structure to improve the electrochemical performance.
  • the conductive component comprises activated carbon having electrical conductivity, natural graphite, artificial graphite, carbon aerogel, carbon fiber, carbon nanotube, graphite oxide, graphene, reduced graphene, carbon black, acetylene black, metal One or more of Ni, metal Cu, compound RuO 2 , compound TiC, polyaniline, polythiophene, and polypyrrole.
  • the conductive component only needs to have good electrical conductivity and can be used to improve the electrochemical performance of the active material.
  • the conductive component herein may also be one or more doped carbon materials of nitrogen, boron, phosphorus, sulfur.
  • a negative electrode for a lithium ion/sodium ion battery comprising: a current collector and a negative active material layer, the negative active material layer being formed on at least one surface of the current collector And comprising an anode active material, wherein the anode active material is an anode active material as defined above.
  • a lithium ion battery comprising a positive electrode, a negative electrode, and a separator disposed between the positive electrode and the negative electrode, wherein the negative electrode is a negative electrode as defined above.
  • a sodium ion battery comprising a positive electrode and a negative electrode And a separator disposed between the positive electrode and the negative electrode, wherein the negative electrode is a negative electrode as defined above.
  • the phosphonium compound prepared by the method of the present invention contains both antimony and phosphorus, and both phosphorus and antimony have high lithium/sodium storage activity, so the phosphonium compound has high lithium/sodium storage capacity, and the test proves that phosphorus
  • the ruthenium compound is used as a negative electrode material for a lithium ion/sodium ion battery, the charge and discharge curve has the advantages of small difference in charge and discharge voltage platform, gentle curve, and the like, and is convenient for commercial application.
  • the partial phosphonium compound of the present invention has a graphite-like layer structure or a solid solution structure, and the test proves that the conductivity of the phosphonium compound having a graphite-like layer structure or a solid solution structure is superior to that of the semiconductor. .
  • the multi-phosphorus compound also contains a metal element other than cerium, which can conduct electrons on the one hand and buffer the volume expansion of the electrode on the other hand, which is advantageous for improving the high rate and cycle life of the battery.
  • an excess of ruthenium is coated on the surface of the phosphonium compound, and the metal ruthenium has high conductivity, and at the same time, a stable interface between the active material and the electrolyte can be formed to improve the battery.
  • Cyclic stability, such electrodes have higher rate performance; excessive phosphorus coating on the surface of the phosphonium compound can further increase the capacity, because the lithium storage/sodium capacity of phosphorus is higher than that of strontium; phosphonium compound and elemental phosphorus
  • the solid solution formed by or/and bismuth has metal conductivity, which also contributes to an improvement in its electrochemical performance.
  • the electron transporting ability of the entire electrode material is greatly improved, and the specific surface area is also increased, which is more favorable for the electrolyte infiltration.
  • the lithium ion/sodium ion transport distance can be shortened. Due to the introduction of conductive components, the particle size of the phosphonium compound becomes smaller or even amorphized. When lithium/sodium is embedded in such an electrode, the volume expansion change is greatly buffered, so that repeated deintercalation does not cause the electrode material to be removed. The fluid is detached and does not cause electrical insulation caused by the pulverization of the active material, thereby avoiding a drastic reduction in cycle performance.
  • the phosphonium compound in the electrode of the invention can be directly obtained by ball milling of the Ge powder and the P powder, and the ball milling method has fewer process steps than the conventional high-pressure synthesis or the high-temperature sintering synthesis method after grinding, and does not require high-temperature operation. simpler.
  • a second composite having a conductive component of C can be prepared.
  • the specific structure of the second composite of conductive component C is carbon-coated.
  • a crystallization material that can be directly mixed with a binder to serve as an electrode eliminates the need to add a conductive agent, which greatly saves the electrode preparation process.
  • the electrode of the present invention has the advantages of high theoretical capacity, high first coulomb efficiency, small difference in charge and discharge voltage platform, excellent cycle characteristics, long life, and the like, and can maintain high discharge capacity, high coulombic efficiency, high magnification, and low voltage platform. It has excellent electrochemical properties and is a promising electrode, which is of great significance for achieving a safe, effective and stable battery.
  • the electrode of the invention mainly comprises Ge, P and a compound consisting of Ge and P, and can be prepared by ball milling. The electrode has abundant raw materials, low price, simple preparation method, convenient promotion and large-scale production, and is an extremely application. Potential for electrodes for lithium-ion and sodium-ion batteries.
  • Figure 5 is a face-scan view of a second composite formed of GeP 5 and C in an embodiment of the present invention, in which (a), (b), (c), and (d) are SEMs of the composite, respectively.
  • Figure 8 is a graph showing the sodium storage performance of GeP contained in the electrode of the embodiment of the present invention.
  • Figure 10 is a graph showing the sodium storage performance of GeP 5 contained in an electrode according to an embodiment of the present invention.
  • the negative electrode active material for a lithium ion/sodium ion secondary battery is a material having various components, and mainly comprises one or more of the following four types of materials:
  • the phosphonium compound comprises a binary integer compound formed of P and Ge, a binary non-ratio compound formed of P and Ge, and a polyphosphonium compound formed by P and Ge and element M;
  • the first complex a composite or solid solution formed by a phosphonium compound and elemental P and/or elemental Ge;
  • a second composite is a complex formed by the phosphonium compound and a conductive component;
  • the third composite is a first complex and A composite formed by a conductive component.
  • the negative electrode material of the present invention will be more specifically described below by way of examples, but the present invention is not limited to these examples.
  • Phosphorus with a purity of 99.8% and strontium with a purity of 99.9% were added to the ball mill tank.
  • the ratio of the ball to the material was 13:1, the rotation speed was 350-600 rpm, and the ball was milled for 2-20 hours to obtain P and Ge.
  • various binary ratio compounds formed by P and Ge can be prepared by the ball milling method, and the phase is detected by X-ray diffraction, and the binary ratio compound has the following Species: GeP, GeP2, GeP3, GeP4, GeP5, Ge2P2, Ge3P, Ge2P3, and Ge3P4.
  • the product may also be a mixture of a plurality of the above binary ratio compounds.
  • the phase of the plurality of substances may be detected by X-ray diffraction. Diffraction peaks.
  • Table 1 shows the binary integer compound formed of P and Ge in the examples of the present invention. The various possible combinations of the nine binary integer compounds are not listed in the table, but other possible combinations not listed in Table 1 cannot be excluded.
  • Fig. 1 is an X-ray diffraction diagram of a GeP prepared by ball milling in an electrode of the present invention, and it can be seen from the figure that all diffraction peaks can correspond to a standard PDF card (the card number is 44-1125). It is indicated that a pure phase GeP is obtained.
  • Table 1 is a partial binary ratio compound formed by P and Ge in the embodiment of the present invention.
  • Example Phase obtained by XRD analysis Example 1 GeP Example 2 GeP 2 Example 3 GeP 3 Example 4 GeP 4 Example 5 GeP 5 Example 6 Ge 2 P 2
  • GeP 5 is an energy spectrum diagram of GeP 5 in the embodiment of the present invention. It is known from the figure that it is composed of elements Ge and P, and the atomic ratio of Ge to P is 1:5, and other small elements such as copper are derived from Do TEM copper mesh, and carbon comes from contaminated carbon.
  • the morphology of GeP 5 is a nanoparticle, which is a secondary particle formed by agglomerating smaller primary particles, such that The formed secondary particles on the one hand facilitate the impregnation of the electrolyte and on the other hand have a higher tap density, which is advantageous for increasing the energy density of the entire electrode.
  • Phosphorus with a purity of 99.8% and strontium with a purity of 99.9% were added to the ball mill tank, and the ratio of the ball to the material was 15:1, the rotation speed was 450 rpm, and the ball was milled for 15 hours to obtain the two formed by P and Ge.
  • Non-integral compound By adjusting the mass ratio of phosphor powder and elemental germanium, various binary non-ratio compounds formed by P and Ge can be prepared by the ball milling method. The compounds are analyzed by X-ray diffraction and analyzed by scanning electron microscopy.
  • the surface scanning function was carried out to analyze the composition, and it was found that the diffraction peaks of the compounds have diffraction peaks of the binary complex compounds formed by P and Ge, and the diffraction peaks of elemental phosphorus and elemental germanium, but the surface of the scanning electron microscope Scanning component analysis function detection and analysis, found that elemental phosphorus, elemental ⁇ uniform distribution, indicating the binary non-ratio compound Divided into solid solution structure. After quantitative component analysis, the following two kinds of binary non-ratio compounds are known:
  • (xiii) a compound having a chemical formula of Ge 1 ⁇ a P 5 ⁇ b , wherein 0 ⁇ a ⁇ 0.2, and 0 ⁇ b ⁇ 0.2, wherein, after preparation by a high-energy ball milling method, Ge 0.8 P 5.2 is confirmed according to experimental analysis. , Ge 1.2 P 4.8 and Ge 0.9 P 5.1 ;
  • Table 2 is a binary non-ratio compound formed by P and Ge in the embodiment of the present invention.
  • various possible ratios in the binary non-ratio compound are not listed one by one, but not Therefore, other possible ratios not listed in Table 2 are excluded.
  • phosphorus powder, bismuth and one or more of Li elemental substance, Si powder, Sn powder, Pb elemental substance, Zn elemental substance, Mn elemental substance, Fe powder, Co powder and Cu powder are mixed together and added to the ball mill.
  • the can was filled with argon gas to obtain the polyphosphorus compound by a ball to ball ratio of 20:1, a rotation speed of 500 rpm, and ball milling for 20 hours.
  • the chemical formula of the multi-phosphorus compound is: Li 5 GeP 3 , ZnGeP 2 , MnGeP 2 , Zn 1-x Mn x GeP 2 .
  • the polyphosphonium compound may also be CdGeP 2 , GexPxS 1-2x , Cd 1-x Mn x GeP 2 , Zn 1-x Mn x GeP 2 .
  • Table 3 lists the polyphosphorus compounds partially formed by P and Ge together with the element M. Only a limited number of polyphosphonium compounds are listed in this table, but other ternary phosphonium compounds not listed are not excluded.
  • Example Phase obtained by XRD analysis Example 36 Li 5 GeP 3 Example 37 ZnGeP 2 Example 38 MnGeP 2 Example 39 Zn 1-x Mn x GeP 2
  • the phosphonium compound prepared above was added to a ball mill tank with a phosphor powder having a purity of 99.8% or a purity of 99.9%, and a ball-to-feed ratio of 18:1, a rotation speed of 700 rpm, and a ball milling time of 19 hours.
  • First complex After X-ray diffraction detection analysis and surface scanning function carried out by scanning electron microscopy, component analysis was carried out, and it was found that the diffraction peak had a peak of elemental phosphorus and elemental ruthenium, and also had a peak of the above-mentioned phosphonium compound.
  • Table 4 is a partial first composite in which only a few first complexes are listed, but other first compounds not listed are therefore not excluded.
  • the phosphonium compound obtained by the above preparation was mixed with a conductive component and then added to a ball mill tank at a ball-to-batch ratio of 19:1, a rotation speed of 400 rpm was determined, and a second composite was obtained by ball milling for 10 hours.
  • the conductive component may be activated carbon having electrical conductivity, natural graphite, graphene, graphite flakes, artificial graphite, carbon aerogel, carbon fiber, carbon nanotubes, graphite oxide, graphene, reduced graphene, conductive carbon black , acetylene black, metal Ni, metal Cu, compound RuO 2 , compound TiC, polyaniline, polythiophene, and polypyrrole, or one or more doped carbon materials of nitrogen, boron, phosphorus, sulfur.
  • Table 5 is a partial second composite in which only a few second composites are listed, but other secondary compounds not listed are therefore not excluded.
  • the composition and size of several conductive components are listed in Table 6, but the components and components not listed in the table are therefore not excluded.
  • the conductive component only needs to have good electrical conductivity, and the conduction for electrons can be used to improve the electrochemical performance of the active material.
  • the conductive component here may also be a nitrogen, boron, phosphorus, sulfur one
  • the one or more doped carbon materials are other materials having electrical conductivity not mentioned in the present invention.
  • Example GeP GeP 2 GeP 3 GeP 5 Conductive component Example 48 / 5 25 60 10
  • Example 52 10 40 / / 50 Example 53 20 5 / 15 60
  • Example 54 20 10 / / 70
  • Example 55 25 10 / 30 35
  • Example 56 / 30 / 10 Example 57 10 10 10 5 65
  • Table 5 is a partial second composite in which only a few second composites are listed, but other secondary compounds not listed are therefore not excluded.
  • the composition and size of several conductive components are listed in Table 6, but the components and components not listed in the table are therefore not excluded.
  • the conductive component only needs to have good electrical conductivity, and the conduction for electrons can be used to improve the electrochemical performance of the active material.
  • the conductive component herein may also be one or more doped carbon materials of nitrogen, boron, phosphorus, sulfur or other electrically conductive materials not mentioned in the present invention.
  • FIG. 4 is an energy spectrum diagram of a second composite formed of GeP 5 and C in the embodiment of the present invention, which shows that the element contains Ge, P, and C, and other small elements such as copper are derived from TEM. Copper net.
  • Figure 5 is a face-scan view of a second composite formed of GeP 5 and C in an embodiment of the present invention, in which (a), (b), (c), and (d) are SEMs of the composite, respectively.
  • the first composite and the conductive component are ball milled, and the third composite is also obtained, and the column in Table 7 Part of the composition and content of the third composite is shown, only a few third composites are given in the table, but other third composites not listed in the table can not be discharged. Further, the sum of the mass percentage of the conductive component, the mass percentage of the phosphonium compound, the mass percentage of the elemental P, and the mass percentage of the elemental Ge in the table is 100%.
  • a lithium ion or sodium ion secondary battery negative electrode is prepared by using the negative electrode active material of the present invention, the negative electrode includes a current collector and a negative electrode active material layer, and the negative electrode active material layer is formed on four surfaces of the current collector, but the negative electrode active material in the present invention
  • the number of layers formed on the surface of the current collector is not particularly limited, and the negative electrode active material layer contains one or more of a phosphonium compound, a first composite, a second composite, and a third composite.
  • the negative electrode prepared by using GeP as the negative electrode active material is subjected to electrochemical performance test to obtain a charge and discharge curve of lithium storage and sodium storage, as shown in FIG. 7 and FIG. 8,
  • FIG. 7 is a GeP in the embodiment of the present invention.
  • the lithium storage performance map of the electrode prepared for the active material has a lithium storage capacity of about 1897 mA h/g, which has a first coulombic efficiency of 90% or more.
  • Figure 8 is this
  • the sodium storage performance of the electrode prepared by using GeP as an active material shows that the sodium storage capacity is about 850 mA h/g, which has a first coulombic efficiency of nearly 90%.
  • the negative electrode prepared by using GeP 5 as the negative electrode active material is subjected to electrochemical performance test to obtain a charge and discharge curve of lithium storage and sodium storage, as shown in FIG. 9 and FIG. 10, and FIG. 9 is an embodiment of the present invention.
  • GeP 5 is a lithium storage performance diagram of an electrode prepared from an active material. As can be seen from the figure, the lithium storage capacity is about 2289 mA h/g, which has a first coulombic efficiency of more than 90%.
  • FIG. 10 is a graph showing the sodium storage performance of an electrode prepared by using GeP 5 as an active material in the embodiment of the present invention. As can be seen from the figure, the sodium storage capacity is about 1250 mA h/g, which has a first coulombic efficiency close to 90%.
  • Table 8 lists the lithium storage capacity of an electrode prepared by using a part of the phosphonium compound and a part of the second composite as an electrode active material.
  • the lithium storage capacity of GeP 5 is the largest in the phosphonium compound, reaching about 2289 mA h/g, and in the second composite, the complex of GeP 5 and C has the largest lithium storage capacity. Approximately 2389 mA h/g. Only a limited number of bismuth compounds and a limited number of second complexes were given in this table, but other phosphonium compounds not listed and other second complexes could not be excluded.
  • Table 9 lists the sodium storage capacity of an electrode prepared by using a part of the phosphonium compound and a part of the second composite as an electrode active material.
  • the sodium storage capacity of GeP 5 is the largest in the phosphonium compound, reaching 1250 mA h/g, and in the second composite, the complex formed by GeP 5 and C has the largest sodium storage capacity, reaching approximately 1300 mA h/g. Only a limited number of phosphonium compounds and a limited number of second complexes were given in this table, but other phosphonium compounds not listed and other second complexes could not be excluded.
  • Table 8 Lithium storage capacity of an electrode prepared by using a partially phosphonium compound and a part of a second composite as an electrode active material.
  • a lithium ion or sodium ion battery prepared by using the above electrode comprising a positive electrode, a negative electrode, and a separator disposed between the positive electrode and the negative electrode, wherein the negative electrode is a negative electrode as defined above, the negative electrode comprising a phosphonium compound,
  • the first composite, the second composite, and the third composite that is, a sodium ion battery or a lithium ion battery including the above electrode, are within the scope of the present invention as long as the electrode contains the above phosphonium compound, A composite, a second composite, and a third composite are all within the scope of the claimed invention.
  • the specific ratio and combination of the size of the conductive component, the specific component of the conductive component, and the specific component and the combination of the conductive component and the compound, or the specific ratio and combination of the compound and the elemental P or the elemental Ge are not limited to the above.
  • the conductive component is preferred, and other conductive materials may also be selected, and the size of the conductive component may be smaller or larger, in principle, and the The mass of the conductive component is 10% to 70% of the total mass of the second/triple composite, and is feasible and limited to the specific values in the above embodiments.
  • the specific ratio of the compound, the first composite, the second composite, and the third composite is not limited.

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  • Secondary Cells (AREA)

Abstract

L'invention porte sur un matériau actif d'électrode négative pour une batterie rechargeable au lithium-ion/sodium-ion, sur une électrode négative et sur une batterie qui se rapportent au domaine technique de l'électrochimie et des batteries. Le matériau actif d'électrode négative comprend un composé à base de germanium et de phosphore et/ou un premier complexe formé par le composé à base de germanium et de phosphore et du phosphore (P) élémentaire et/ou du germanium (Ge) élémentaire et/ou un deuxième complexe formé par le composé à base de germanium et de phosphore et des composants conducteurs et/ou un troisième complexe formé par le premier complexe et des composants conducteurs. L'électrode négative présente pour avantages une capacité spécifique élevée, un rendement coulombien initial élevé, une petite différence de plate-forme de tension de charge-décharge et de bonnes performances de charge-décharge de courant élevé.
PCT/CN2015/089690 2015-01-08 2015-09-16 Matériau actif d'électrode négative pour une batterie au lithium-ion/sodium-ion, électrode négative et batterie WO2016110127A1 (fr)

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