WO2016008350A1 - 一种层状含铜氧化物材料及其制备方法和用途 - Google Patents

一种层状含铜氧化物材料及其制备方法和用途 Download PDF

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WO2016008350A1
WO2016008350A1 PCT/CN2015/081802 CN2015081802W WO2016008350A1 WO 2016008350 A1 WO2016008350 A1 WO 2016008350A1 CN 2015081802 W CN2015081802 W CN 2015081802W WO 2016008350 A1 WO2016008350 A1 WO 2016008350A1
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oxide material
containing oxide
layered copper
sodium
precursor
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French (fr)
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胡勇胜
李云明
徐淑银
王跃生
陈立泉
黄学杰
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Institute of Physics of CAS
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Priority to KR1020157037258A priority Critical patent/KR20170068354A/ko
Priority to EP15821926.1A priority patent/EP3021386B1/en
Priority to JP2016544722A priority patent/JP6165345B2/ja
Priority to US14/913,115 priority patent/US20160211516A1/en
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    • C01G53/42—Complex oxides containing nickel and at least one other metal element containing alkali metals, e.g. LiNiO2
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    • C01G53/44—Complex oxides containing nickel and at least one other metal element containing alkali metals, e.g. LiNiO2 containing manganese
    • C01G53/50—Complex oxides containing nickel and at least one other metal element containing alkali metals, e.g. LiNiO2 containing manganese of the type (MnO2)n-, e.g. Li(NixMn1-x)O2 or Li(MyNixMn1-x-y)O2
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    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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    • 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
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
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    • 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
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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    • 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
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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    • H01M2220/10—Batteries in stationary systems, e.g. emergency power source in plant
    • 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
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    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Definitions

  • the invention relates to the technical field of materials, in particular to a layered copper-containing oxide material, a preparation method thereof and use thereof.
  • the current secondary batteries mainly include nickel-hydrogen batteries, nickel-cadmium batteries, lead-acid batteries, and lithium ion batteries.
  • Lithium-ion batteries are widely used due to their small size, light weight, high specific energy, no memory effect, no pollution, small self-discharge, and long cycle life.
  • lithium-ion batteries cost up. High, unable to meet the low-cost requirements of large-scale applications, and having similar physicochemical properties with the same main family of sodium, rich in content and low cost. Therefore, the development of sodium ion secondary batteries as a large-scale energy storage device has once again attracted people's attention.
  • a NASICON structure with high sodium ion conductance is a phosphate positive electrode material of interest, typically Na 3 V 2 (PO 4 ) 3 .
  • Hu Yongsheng et al. proposed carbon coating for the first time and optimized the electrolyte.
  • the platform capacity of 3.4V reached 107 mAh/g, which significantly improved the cycle stability [Electrochem.Commun., 2012, 14, 86-89, Adv .Energy Mater., 2013, 3, 156-160].
  • Another representative is Na 3 V 2 (PO 4 ) 2 F 3 with the highest average voltage, with an average voltage of 3.95 V and a capacity of 120 mAh/g [J. Mater. Chem., 2012, 22, 20535- 20541].
  • Na 3 V 2 (PO 4 ) 3 exhibits excellent performance, its further development is hindered by the insufficient vanadium resources and the toxicity of pentavalent vanadium.
  • the oxide positive electrode material is divided into two types, a layered type and a tunnel type.
  • the structure oxide of the tunnel is mainly Na 0.44 MnO 2 with S-type large channel.
  • Cao et al. studied the Na 0.44 MnO 2 nanowire, and the capacity retention rate was 77% after 1000 cycles of 0.5C, showing excellent cycle performance [Adv .Mater., 2011, 23, 3155-3160], but its first week charge only half of the capacity, the other half of the capacity comes from the metal sodium negative electrode, and in practical applications, the negative electrode does not provide sodium, so it is difficult to apply.
  • the layered oxide can be classified into a P2 phase and an O3 phase according to the environment in which the sodium ion is placed and the manner in which oxygen is deposited [Physical B&C, 1980, 99, 81-85].
  • the electrochemical cycle performance of the O3 phase is poor, and it is sensitive to air and water, and is difficult to apply.
  • the P2 phase has not only a high capacity, but also has a large space in the sodium ion, and has good stability during the electrochemical cycle, but most of it
  • the P2 phase material is unstable in air.
  • Lu et al. prepared a P 2 phase Na 2/3 Ni 1/3 Mn 2/3 O 2 material and characterized its electrochemical properties. It has a 160 mAh/g between 2.0V and 4.5V.
  • the capacity [ZHLu and JRDahn, J. Electrochem. Soc., 2001, 148, A1225-A1229], but its electrochemical curve shows multiple platforms, the cycle stability is very poor.
  • Embodiments of the present invention provide a layered copper-containing oxide material, a preparation method thereof and use thereof.
  • the layered copper-containing oxide material is simple in preparation, rich in raw material resources, low in cost, and is a non-polluting green material, and can be applied to a positive electrode active material of a sodium ion secondary battery, and the layered layer of the invention is applied.
  • the sodium ion secondary battery containing copper oxide material has high working voltage and first-cycle coulombic efficiency, stable in air, stable circulation, good safety performance, and can be used for solar power generation, wind power generation, smart grid peak shaving, distribution Large-scale energy storage equipment for power stations, backup power sources, or communication base stations.
  • an embodiment of the present invention provides a layered copper-containing oxide material having a chemical formula of: Na 0.68+a Ni b Cu c M d Mn e O 2+ ⁇ ;
  • Ni, Cu, and Mn are transition metal elements, and M is an element for doping substitution of transition metal sites; and Ni, Cu, Mn, and M form an octahedral structure with six nearest oxygen atoms, respectively,
  • the octahedral structure is arranged side by side to form a transition metal layer;
  • the alkali metal ion Na + is located between every two layers of the transition metal layer;
  • the M is specifically Mg 2+ , Mn 2+ , Zn 2+ , Co 2+ , Al 3+ , B 3+ , Cr 3+ , Mn 3+ , Co 3+ , V 3+ , Zr 4+ , Ti 4+ , Sn 4+ , Mo 4+ , Ru 4+ , Nb 4+ , Sb 5 + , one or more of Nb 5+ , Mo 6+ , Te 6+ ;
  • the valence state of the M is m, and the m is specifically monovalent, divalent, trivalent
  • the layered copper-containing oxide material is used for a positive electrode active material of a sodium ion secondary battery.
  • the embodiment of the present invention provides a method for preparing a layered copper-containing oxide material according to the above first aspect, which is a solid phase method, comprising:
  • the stoichiometric amount of sodium sodium of 102% to 108% by weight of the desired sodium and the oxides of the desired stoichiometric amounts of nickel oxide, copper oxide, manganese dioxide and M are mixed in proportion to form a precursor;
  • the M is specifically Mg 2+ , Mn 2+ , Zn 2+ , Co 2+ , Al 3+ , B 3+ , Cr 3+ , Mn 3+ , Co 3+ , V 3+ , Zr 4+ , Ti 4+ , Sn 4+ , Mo
  • the precursor is uniformly mixed by a ball milling method to obtain a precursor powder
  • the precursor powder is placed in a muffle furnace and heat-treated in an air atmosphere at 750 ° C to 1000 ° C for 10 to 24 hours;
  • the heat-treated precursor powder is ground to obtain the layered copper-containing oxide material.
  • the present invention provides a method for preparing a layered copper-containing oxide material according to the above first aspect, which is a spray drying method, comprising:
  • the stoichiometric amount of sodium sodium of 102% to 108% by weight of the desired sodium and the oxides of the desired stoichiometric amounts of nickel oxide, copper oxide, manganese dioxide and M are mixed in proportion to form a precursor;
  • the M is specifically Mg 2+ , Mn 2+ , Zn 2+ , Co 2+ , Al 3+ , B 3+ , Cr 3+ , Mn 3+ , Co 3+ , V 3+ , Zr 4+ , Ti 4+ , Sn 4+ , Mo
  • the precursor powder is placed in a muffle furnace and heat-treated in an air atmosphere at 750 ° C to 1000 ° C for 10 to 24 hours;
  • the heat-treated precursor powder is ground to obtain the layered copper-containing oxide material.
  • the present invention provides a method for preparing a layered copper-containing oxide material according to the above first aspect, which is a sol-gel method, comprising:
  • the stoichiometric amount of sodium required from 102% to 108% by weight of sodium acetate, the nitrate of the desired stoichiometric transition metal and the nitrate of the doping element M are dissolved in a volume of deionized water and magnetically stirred at 80 ° C.
  • M is specifically Mg 2+ , Mn 2+ , Zn 2+ , Co 2+ , Al 3+ , B 3+ , Cr 3+ , Mn 3 + , Co 3+ , V 3+ , Zr 4+ , Ti 4+ , Sn 4+ , Mo 4+ , Ru 4+ , Nb 4+ , Sb 5+ , Nb 5+ , Mo 6+ , Te 6+
  • M is specifically Mg 2+ , Mn 2+ , Zn 2+ , Co 2+ , Al 3+ , B 3+ , Cr 3+ , Mn 3 + , Co 3+ , V 3+ , Zr 4+ , Ti 4+ , Sn 4+ , Mo 4+ , Ru 4+ , Nb 4+ , Sb 5+ , Nb 5+ , Mo 6+ , Te 6+
  • M is specifically Mg 2+ , Mn 2+ , Zn 2+ , Co 2+ , Al 3+
  • the precursor gel is placed in a crucible, and calcined in an air atmosphere at 250 ° C to 500 ° C for 2 hours;
  • the heat-treated precursor powder is ground to obtain the layered copper-containing oxide material.
  • the transition metal comprises: Ni, Cu, and Mn.
  • the embodiment of the present invention provides the use of the layered copper-containing oxide material prepared by the method of the second aspect, the third aspect or the fourth aspect, wherein the layered copper-containing oxide material For solar power generation, wind power generation, smart grid peak shaving, distributed power station, backup power supply Or a large-scale energy storage device of a communication base station.
  • an embodiment of the present invention provides a positive electrode tab of a sodium ion secondary battery, and the positive electrode tab includes:
  • the embodiment of the invention provides a sodium ion secondary battery comprising the positive electrode tab of the sixth aspect.
  • the embodiment of the present invention provides the use of the sodium ion secondary battery according to the seventh aspect, wherein the sodium ion secondary battery is used for solar power generation, wind power generation, smart grid peak shaving, and distributed power station Large-scale energy storage equipment for backup power or communication base stations.
  • the layered copper-containing oxide material provided by the embodiment of the invention is simple in preparation, rich in raw material resources, low in cost, and is a non-polluting green material, and can be applied to a cathode active material of a sodium ion secondary battery, and the layered copper-containing material of the invention is applied.
  • Sodium ion secondary battery with oxide material, high operating voltage and first week Coulomb efficiency, stable cycle, good safety performance can be used for solar power generation, wind power generation, smart grid peak shaving, distributed power station, backup power supply or communication Large-scale energy storage equipment for base stations.
  • Example 1 is an XRD pattern of a plurality of layered copper-containing oxide materials having different element molar percentages according to Example 1 of the present invention
  • FIG. 2 is a flow chart of a method for preparing a layered copper-containing oxide material according to Embodiment 2 of the present invention
  • FIG. 3 is a flow chart of a method for preparing another layered copper-containing oxide material according to Embodiment 3 of the present invention.
  • FIG. 4 is a flow chart of a method for preparing a layered copper-containing oxide material according to Embodiment 4 of the present invention.
  • Figure 5 is an SEM image of Na 0.68 Ni 0.23 Cu 0.11 Mn 0.66 O 2 provided in Embodiment 5 of the present invention.
  • FIG. 6 is a graph showing charge and discharge curves of a sodium ion battery according to Embodiment 5 of the present invention.
  • FIG. 7 is a graph showing charge and discharge curves of a sodium ion battery according to Embodiment 6 of the present invention.
  • Embodiment 8 is a graph showing charge and discharge curves of a sodium ion battery according to Embodiment 7 of the present invention.
  • Embodiment 9 is a charging and discharging graph of a sodium ion battery according to Embodiment 8 of the present invention.
  • FIG. 10 is a graph showing charge and discharge curves of a sodium ion battery according to Embodiment 9 of the present invention.
  • FIG. 11 is a graph showing charge and discharge curves of a sodium ion battery according to Embodiment 10 of the present invention.
  • Embodiment 13 is a graph showing charge and discharge curves of a sodium ion battery according to Embodiment 12 of the present invention.
  • Figure 14 is a SEM image of Na 0.68 Ni 0.23 Cu 0.11 Ti 0.16 Mn 0.5 O 2 provided in Example 13 of the present invention.
  • FIG. 16 is a graph showing charge and discharge curves of a sodium ion battery according to Embodiment 14 of the present invention.
  • Embodiment 1 of the present invention provides a layered copper-containing oxide material having a chemical formula of: Na 0.68+a Ni b Cu c M d Mn e O 2+ ⁇ ;
  • Ni, Cu, and Mn are transition metal elements
  • M is an element for doping substitution of a transition metal site
  • the M is specifically Mg 2+ , Mn 2+ , Zn 2+ , Co 2+ , Al 3+ , B 3+ , Cr 3+ , Mn 3+ , Co 3+ , V 3+ , Zr 4+ , Ti 4+ , Sn 4+ , Mo 4+ , Ru 4+ , Nb 4+ , Sb 5+ , Nb 5 + , one or more of Mo 6+ , Te 6+ ;
  • the valence state of the M is m, and the m is specifically monovalent, divalent, trivalent, tetravalent, pentavalent or hexavalent;
  • Ni, Cu, M, and Mn form an octahedral structure with the nearest six oxygen atoms, and a plurality of octahedral structures are arranged side by side.
  • the cloth constitutes a transition metal layer, and an alkali metal ion Na + is located between each two transition metal layers to form a layered structure.
  • FIG. 1 An X-ray diffraction (XRD) pattern of a plurality of layered copper-containing oxide materials with different element mole percentages is given in FIG. 1. It can be seen from the XRD pattern that the Na 0.68+ provided in this embodiment a Ni b Cu c M d Mn e O 2+ ⁇ crystal structure is an oxide of a layered structure of the P2 phase.
  • XRD X-ray diffraction
  • the layered copper-containing oxide material provided by the embodiment is simple in preparation, rich in raw material resources, low in cost, and is a non-polluting green material, and can be applied to a positive electrode active material of a sodium ion secondary battery, and the layered content of the invention is applied.
  • the copper ion material is used as a positive electrode active material for a sodium ion secondary battery, which has a high working voltage and a first week coulombic efficiency, stable air, stable circulation, and good safety performance.
  • This embodiment provides a method for preparing a layered copper-containing oxide material, specifically a solid phase method, as shown in FIG. 2, comprising:
  • Step 201 mixing the stoichiometric amount of sodium sodium of 102% to 108% by weight of the desired sodium and the oxides of the desired stoichiometric amounts of nickel oxide, copper oxide, manganese dioxide and M into a precursor;
  • the M may be Mg 2+ , Mn 2+ , Zn 2+ , Co 2+ , Al 3+ , B 3+ , Cr 3+ , Mn 3+ , Co 3+ , V 3+ , Zr 4 + , one or more of Ti 4+ , Sn 4+ , Mo 4+ , Ru 4+ , Nb 4+ , Sb 5+ , Nb 5+ , Mo 6+ , Te 6+ .
  • Step 202 uniformly mixing the precursors by a ball milling method to obtain a precursor powder
  • Step 203 the precursor powder is placed in a muffle furnace, heat treatment in an air atmosphere of 750 ° C ⁇ 1000 ° C for 10 to 24 hours;
  • step 204 the heat-treated precursor powder is ground to obtain the layered copper-containing oxide material.
  • the method for preparing the layered copper-containing oxide material provided in this embodiment can be used for preparing the layered copper-containing oxide material described in the above embodiment 1.
  • the method provided in this embodiment is simple, easy to implement, low in cost, and suitable for applications that can be manufactured on a large scale.
  • This embodiment provides a method for preparing a layered copper-containing oxide material, specifically a spray drying method, as shown in FIG. 3, comprising:
  • Step 301 the stoichiometric amount of sodium carbonate of 102% to 108% by weight of the desired sodium and the oxides of the desired stoichiometric amounts of nickel oxide, copper oxide, manganese dioxide and M are used as precursors;
  • the M may be Mg 2+ , Mn 2+ , Zn 2+ , Co 2+ , Al 3+ , B 3+ , Cr 3+ , Mn 3+ , Co 3+ , V 3+ , Zr 4 + , one or more of Ti 4+ , Sn 4+ , Mo 4+ , Ru 4+ , Nb 4+ , Sb 5+ , Nb 5+ , Mo 6+ , Te 6+ .
  • Step 302 adding the ethanol or water to the precursor and stirring to form a slurry
  • Step 303 spray drying the slurry to obtain a precursor powder
  • step 304 the precursor powder is placed in a muffle furnace and heat-treated in an air atmosphere of 750 ° C to 1000 ° C for 10 to 24 hours.
  • step 305 the heat-treated precursor powder is ground to obtain the layered copper-containing oxide material.
  • the method for preparing the layered copper-containing oxide material provided in this embodiment can be used for preparing the layered copper-containing oxide material described in the above embodiment 1.
  • the method provided in this embodiment is simple, easy to implement, low in cost, and suitable for applications that can be manufactured on a large scale.
  • This embodiment provides a method for preparing a layered copper-containing oxide material, specifically a sol-gel method, as shown in FIG. 4, comprising:
  • Step 401 dissolving a stoichiometric amount of sodium sodium of 102% to 108% by weight of sodium, a stoichiometric amount of a transition metal nitrate, and a nitrate of a doping element M in a stoichiometric amount of deionized water.
  • the transition metal may include: Ni, Cu, and Mn.
  • M is an element for doping substitution of transition metal sites, specifically Mg 2+ , Mn 2+ , Zn 2+ , Co 2+ , Al 3+ , B 3+ , Cr 3+ , Mn 3+ , Co 3+
  • Step 402 placing the precursor gel in a crucible, and preheating for 2 hours in an air atmosphere of 250 ° C to 500 ° C;
  • Step 403 further heat treatment at 750 ° C ⁇ 1000 ° C for 5 to 24 hours;
  • step 404 the heat-treated precursor powder is ground to obtain the layered copper-containing oxide material.
  • the method for preparing the layered copper-containing oxide material provided in this embodiment can be used for preparing the layered copper-containing oxide material described in the above embodiment 1.
  • the method provided in this embodiment is simple, easy to implement, low in cost, and suitable for applications that can be manufactured on a large scale.
  • Example 2 of the present invention The specific process for preparing the layered copper-containing oxide material by the method provided in Example 2 of the present invention, and the method and battery characteristics for applying the same to the secondary battery will be described below by way of a plurality of specific examples.
  • the layered copper-containing oxide material is prepared by the solid phase method described in the foregoing embodiment 2.
  • Na 2 CO 3 (analytical grade), NiO (analytical grade), CuO and MnO 2 were mixed in the desired stoichiometric ratio; ground in an agate mortar for half an hour to obtain a precursor; transfer of the precursor substance to Al 2 O After 3 hours in a muffle furnace at 900 ° C for 15 hours, a layered copper-containing oxide material of black powder, Na 0.68 Ni 0.23 Cu 0.11 Mn 0.66 O 2 , was obtained.
  • the XRD pattern is shown in Fig. 1, and the XRD pattern is seen.
  • the crystal structure of Na 0.68 Ni 0.23 Cu 0.11 Mn 0.66 O 2 is an oxide of a P2 phase layer structure.
  • the layered copper-containing oxide material prepared above was used as an active material of a battery positive electrode material for the preparation of a sodium ion battery.
  • the specific steps are as follows: the prepared Na 0.68 Ni 0.23 Cu 0.11 Mn 0.66 O 2 powder is mixed with acetylene black and the binder polyvinylidene fluoride (PVDF) according to a mass ratio of 80:10:10, and an appropriate amount of N-A is added.
  • PVDF binder polyvinylidene fluoride
  • N-A N-A pyrrolidone
  • a pyrrolidone (NMP) solution is ground in a dry environment at normal temperature to form a slurry, and then the slurry is uniformly coated on a current collector aluminum foil and dried under an infrared lamp to be cut into a (8 ⁇ 8) mm 2 pole. sheet.
  • the pole pieces were dried under vacuum at 100 ° C for 10 hours and then transferred to a glove box for use.
  • the assembly of the simulated battery was carried out in a glove box of an Ar atmosphere, using sodium metal as a counter electrode and a NaClO 4 /diethyl carbonate (EC:DEC) solution as an electrolyte to assemble a CR2032 button cell.
  • the charge and discharge test was performed at a C/10 current density using a constant current charge and discharge mode. Under the condition that the discharge cut-off voltage is 2.5V and the charge cut-off voltage is 4.2V, the test results are shown in Fig. 6.
  • the charge-discharge cycle curves of the first week, the third week, and the fifth week are shown in Fig. 6. It can be seen that the first-cycle discharge specific capacity is up to 88.5 mAh/g, and the first week coulombic efficiency is about 87.6%. Very stable.
  • the layered copper-containing oxide material is prepared by the solid phase method described in the foregoing embodiment 2.
  • Example 5 The specific preparation procedure of this example is the same as that of Example 5, but the stoichiometry of the precursor compounds Na 2 CO 3 (analytical grade), NiO (analytical grade), CuO and MnO 2 used is different from that in Example 5, and a black powder is obtained.
  • the layered copper-containing oxide material Na 0.68 Ni 0.28 Cu 0.06 Mn 0.66 O 2 .
  • the layered copper-containing oxide material prepared above was used as an active material of a battery positive electrode material for the preparation of a sodium ion battery, and subjected to an electrochemical charge and discharge test.
  • the preparation process and test method are the same as those in Example 5.
  • the test voltage range is from 2.5V to 4.2V, and the test results are shown in Figure 7.
  • the charge and discharge curves for the first, third, and fifth weeks are shown in FIG. It can be seen that the first week discharge specific capacity can reach 86.4 mAh / g, the first week Coulomb efficiency is about 88.4%, and has good cycle stability.
  • the layered copper-containing oxide material is prepared by the solid phase method described in the foregoing embodiment 2.
  • Example 5 The specific preparation procedure of this example is the same as that of Example 5, but the stoichiometry of the precursor compounds Na 2 CO 3 (analytical grade), NiO (analytical grade), CuO, MnO 2 and MgO used is different from that in Example 5, and black is obtained.
  • the layered copper-containing oxide material prepared above was used as an active material of a battery positive electrode material for the preparation of a sodium ion battery, and subjected to an electrochemical charge and discharge test.
  • the preparation process and test method are the same as those in Example 5.
  • the test voltage range is from 2.5V to 4.2V, and the test results are shown in Figure 8.
  • the charge and discharge curves for the first, third, and fifth weeks are shown in FIG. It can be seen that the first week discharge specific capacity can reach 84.3 mAh / g, the first week Coulomb efficiency is about 91.3%, and has good cycle stability.
  • the layered copper-containing oxide material is prepared by the solid phase method described in the foregoing embodiment 2.
  • the specific preparation procedure of this example is the same as that of Example 5, but the stoichiometry of the precursor compounds Na 2 CO 3 (analytical grade), NiO (analytical grade), CuO, MnO 2 and ZnO used is different from that in Example 5, and black is obtained.
  • the layered copper-containing oxide material of the powder was Na 0.68 Ni 0.22 Cu 0.08 Zn 0.04 Mn 0.66 O 2 .
  • the layered copper-containing oxide material prepared above was used as an active material of a battery positive electrode material for the preparation of a sodium ion battery, and subjected to an electrochemical charge and discharge test.
  • the preparation process and test method are the same as those in Example 5.
  • the test voltage range is from 2.5V to 4.2V, and the test results are shown in Figure 9.
  • the charge and discharge curves for the first, third, and fifth weeks are shown in FIG. It can be seen that the first week discharge specific capacity can reach 91.2 mAh / g, the first week Coulomb efficiency is about 89.6%.
  • the layered copper-containing oxide material is prepared by the solid phase method described in the foregoing embodiment 2. material.
  • Example 5 The specific preparation procedure of this example is the same as that of Example 5, but the stoichiometry of the precursor compounds Na 2 CO 3 (analytical grade), NiO (analytical grade), CuO, MnO 2 and B 2 O 3 used is different from that in Example 5.
  • the layered copper-containing oxide material obtained as a black powder was Na 0.68 Ni 0.21 Cu 0.10 B 0.06 Mn 0.63 O 2 .
  • the layered copper-containing oxide material prepared above was used as an active material of a battery positive electrode material for the preparation of a sodium ion battery, and subjected to an electrochemical charge and discharge test.
  • the preparation process and test method are the same as those in Example 5.
  • the test voltage range is from 2.5V to 4.2V, and the test results are shown in Figure 10.
  • the charge and discharge curves for the first, third, and fifth weeks are shown in FIG. It can be seen that the first week discharge specific capacity can reach 88.3 mAh / g, the first week Coulomb efficiency is about 93.6%, and has good cycle stability.
  • the layered copper-containing oxide material prepared by the solid phase method described in the foregoing embodiment 2 is used.
  • Example 5 The specific preparation procedure of this example is the same as that of Example 5, but the stoichiometry of the precursor compounds Na 2 CO 3 (analytical grade), NiO (analytical grade), CuO, MnO 2 and Al 2 O 3 used is different from that in Example 5.
  • the layered copper-containing oxide material obtained as a black powder was Na 0.68 Ni 0.24 Cu 0.08 Al 0.04 Mn 0.64 O 2 .
  • the layered copper-containing oxide material prepared above was used as an active material of a battery positive electrode material for the preparation of a sodium ion battery, and subjected to an electrochemical charge and discharge test.
  • the preparation process and test method are the same as those in Example 5.
  • the test voltage range is 2.5V to 4.2V, and the test results are shown in Figure 11.
  • the charge and discharge curves for the first, third, and fifth weeks are shown in FIG. It can be seen that the first week discharge specific capacity can reach 71.5 mAh / g, the first week Coulomb efficiency is about 92.8%, and has good cycle stability.
  • the layered copper-containing oxide material is prepared by the solid phase method described in the foregoing embodiment 2.
  • Example 5 The specific preparation procedure of this example is the same as that of Example 5, but the stoichiometry of the precursor compounds Na 2 CO 3 (analytically pure), NiO (analytical grade), CuO, MnO 2 and Co 2 O 3 used is different from that in Example 5.
  • the layered copper-containing oxide material obtained as a black powder was Na 0.68 Ni 0.20 Cu 0.10 Co 0.08 Mn 0.62 O 2 , and its XRD pattern is shown in FIG.
  • the layered copper-containing oxide material prepared above was used as an active material of a battery positive electrode material for the preparation of a sodium ion battery, and subjected to an electrochemical charge and discharge test.
  • the preparation process and test method are the same as those in Example 5.
  • the test voltage range is from 2.5V to 4.2V, and the test results are shown in Figure 12.
  • the charge and discharge curves for the first, third, and fifth weeks are shown in FIG. It can be seen that the first week discharge specific capacity can reach 73 mAh / g, the first week Coulomb efficiency is about 85.7%, and has good cycle stability.
  • the layered copper-containing oxide material is prepared by the solid phase method described in the foregoing embodiment 2.
  • Example 5 The specific preparation procedure of this example is the same as that of Example 5, but the stoichiometry of the precursor compounds Na 2 CO 3 (analytical grade), NiO (analytical grade), CuO, MnO 2 and Fe 2 O 3 used is different from that in Example 5.
  • the layered copper-containing oxide material obtained as a black powder was Na 0.68 Ni 0.25 Cu 0.06 Fe 0.06 Mn 0.63 O 2 , and its XRD pattern is shown in FIG.
  • the layered copper-containing oxide material prepared above was used as an active material of a battery positive electrode material for the preparation of a sodium ion battery, and subjected to an electrochemical charge and discharge test.
  • the preparation process and test method are the same as those in Example 5.
  • the test voltage range is from 2.5V to 4.2V, and the test results are shown in Figure 13.
  • the charge and discharge curves for the first, second, and third weeks are shown in FIG. It can be seen that the first week discharge specific capacity can reach 83.5 mAh / g, the first week Coulomb efficiency is about 84.6%, and has good cycle stability.
  • the layered copper-containing oxide material is prepared by the solid phase method described in the foregoing embodiment 2.
  • the specific preparation procedure of this example is the same as that of Example 5, but the stoichiometry of the precursor compounds Na 2 CO 3 (analytical purity), NiO (analytical grade), CuO, MnO 2 and TiO 2 used is different from that in Example 5,
  • the layered copper-containing oxide material of the black powder is Na 0.68 Ni 0.23 Cu 0.11 Ti 0.16 Mn 0.50 O 2 .
  • FIG 14 is a Na 0.68 Ni 0.23 Cu 0.11 Ti 0.16 Mn 0.50 O 2 a scanning electron microscope (SEM) of FIG, it can be seen from the figure, Na 0.68 Ni 0.23 Cu 0.11 Ti 0.16 Mn 0.50 O 2 particle size distribution of from several major Micron to a few ten microns.
  • SEM scanning electron microscope
  • the layered copper-containing oxide material prepared above was used as an active material of a battery positive electrode material for the preparation of a sodium ion battery, and subjected to an electrochemical charge and discharge test.
  • the preparation process and test method are the same as those in Example 5.
  • the test voltage range is from 2.5V to 4.2V, and the test results are shown in Figure 15.
  • the charge and discharge curves for the first, third, and fifth weeks are shown in FIG. It can be seen that the first week discharge specific capacity can reach 103.2 mAh / g, the first week Coulomb efficiency is about 87%, and has good cycle stability.
  • the layered copper-containing oxide material is prepared by the solid phase method described in the foregoing embodiment 2.
  • the specific preparation procedure of this example is the same as that of Example 5, except that the precursor compounds Na 2 CO 3 (analytical grade), NiO (analytical grade), CuO, MnO 2 and TiO 2 have a stoichiometric ratio different from that of Example 5, and a black color is obtained.
  • the powdered layered copper-containing oxide material was Na 0.68 Ni 0.28 Cu 0.06 Ti 0.16 Mn 0.50 O 2 .
  • the layered copper-containing oxide material prepared above was used as an active material of a battery positive electrode material for the preparation of a sodium ion battery, and subjected to an electrochemical charge and discharge test.
  • the preparation process and test method are the same as those in Example 5.
  • the test voltage range is from 2.5V to 4.2V, and the test results are shown in Figure 16.
  • the charge and discharge curves for the first, second, and third weeks are shown in FIG. It can be seen that the first week discharge specific capacity can reach 106.2 mAh / g, the first week Coulomb efficiency is about 84.9%.
  • the layered copper-containing oxide material is prepared by the solid phase method described in the foregoing embodiment 2.
  • Example 5 The specific preparation steps of this example are the same as those of Example 5, except that the precursor compounds Na 2 CO 3 (analytical grade), NiO (analytical grade), CuO, MnO 2 and Mn 2 O 3 have stoichiometric ratios different from that of Example 5.
  • the layered copper-containing oxide material obtained as a black powder was Na 0.68 Ni 0.23 Cu 0.08 Mn 0.69 O 2 .
  • the layered copper-containing oxide material prepared above was used as an active material of a battery positive electrode material for the preparation of a sodium ion battery, and subjected to an electrochemical charge and discharge test.
  • the preparation process and test method are the same as those in Example 5.
  • the test voltage range is from 2.5V to 4.2V.
  • the results are shown in Table 1 below.
  • the layered copper-containing oxide material is prepared by the solid phase method described in the foregoing embodiment 2.
  • Example 5 The specific preparation steps of this example are the same as those of Example 5, except that the precursor compounds Na 2 CO 3 (analytical grade), NiO (analytical grade), CuO, MnO 2 and V 2 O 3 have stoichiometric ratios different from those of Example 5.
  • the layered copper-containing oxide material obtained as a black powder was Na 0.68 Ni 0.22 Cu 0.08 V 0.08 Mn 0.62 O 2 .
  • the layered copper-containing oxide material prepared above was used as an active material of a battery positive electrode material for the preparation of a sodium ion battery, and subjected to an electrochemical charge and discharge test.
  • the preparation process and test method are the same as those in Example 5.
  • the test voltage range is from 2.5V to 4.2V.
  • the results are shown in Table 1 below.
  • the layered copper-containing oxide material is prepared by the solid phase method described in the foregoing embodiment 2.
  • the specific preparation procedure of this example is the same as that of Example 5, except that the precursor compounds Na 2 CO 3 (analytical grade), NiO (analytical grade), CuO, MnO 2 and SnO 2 have a stoichiometric ratio different from that of Example 5, and a black color is obtained.
  • the layered copper-containing oxide material of the powder was Na 0.68 Ni 0.24 Cu 0.10 Mn 0.54 Sn 0.12 O 2 .
  • the layered copper-containing oxide material prepared above was used as an active material of a battery positive electrode material for the preparation of a sodium ion battery, and subjected to an electrochemical charge and discharge test.
  • the preparation process and test method are the same as those in Example 5.
  • the test voltage range is from 2.5V to 4.2V.
  • the results are shown in Table 1 below.
  • the layered copper-containing oxide material is prepared by the solid phase method described in the foregoing embodiment 2.
  • Example 5 The specific preparation steps of this example are the same as those of Example 5, except that the precursor compounds Na 2 CO 3 (analytical grade), NiO (analytical grade), CuO, MnO 2 and Nb 2 O 5 stoichiometric ratios are different from that of Example 5.
  • the layered copper-containing oxide material obtained as a black powder was Na 0.68 Ni 0.26 Cu 0.10 Mn 0.60 Nb 0.04 O 2 .
  • the layered copper-containing oxide material prepared above was used as an active material of a battery positive electrode material for the preparation of a sodium ion battery, and subjected to an electrochemical charge and discharge test.
  • the preparation process and test method are the same as those in Example 5.
  • the test voltage range is from 2.5V to 4.2V.
  • the results are shown in Table 1 below.
  • the layered copper-containing oxide material is prepared by the solid phase method described in the foregoing embodiment 2.
  • the specific preparation procedure of this example is the same as that of Example 5, except that the precursor compounds Na 2 CO 3 (analytical grade), NiO (analytical grade), CuO and MnO 2 have stoichiometric ratios different from that of Example 5 to obtain a layer of black powder.
  • the copper-containing oxide material is Na 0.72 Ni 0.24 Cu 0.12 Mn 0.64 O 2 .
  • the layered copper-containing oxide material prepared above was used as an active material of a battery positive electrode material for the preparation of a sodium ion battery, and subjected to an electrochemical charge and discharge test.
  • the preparation process and test method are the same as those in Example 5.
  • the test voltage range is from 2.5V to 4.2V.
  • the results are shown in Table 1 below.
  • the layered copper-containing oxide material is prepared by the solid phase method described in the foregoing embodiment 2.
  • the specific preparation procedure of this example is the same as that of Example 5, but the precursor compounds Na 2 CO 3 (analytical grade), NiO (analytical grade), CuO, MnO 2 and MgO stoichiometric ratio are different from those of Example 5, and a black powder is obtained.
  • the layered copper-containing oxide material is Na 0.70 Ni 0.22 Cu 0.08 Mg 0.05 Mn 0.65 O 2 .
  • the layered copper-containing oxide material prepared above was used as an active material of a battery positive electrode material for the preparation of a sodium ion battery, and subjected to an electrochemical charge and discharge test.
  • the preparation process and test method are the same as those in Example 5.
  • the test voltage range is from 2.5V to 4.2V.
  • the results are shown in Table 1 below.
  • Examples 5-20 can only be applied to the preparation of materials by the solid phase method provided in Example 2 of the present invention, and those skilled in the art can easily think of the spray drying method provided in Example 3 of the present invention or the sol provided in Example 4.
  • a layered copper-containing oxide material obtained in the above Examples 5-20 was prepared by a gel method.
  • the layered copper-containing oxide material provided in the above embodiments of the present invention is simple in preparation, rich in raw material resources, low in cost, and is a non-polluting green material, and can be used as a positive electrode active material of a sodium ion secondary battery for a sodium ion secondary battery.
  • the sodium ion secondary battery thus prepared has a high working voltage and first-cycle coulombic efficiency, stable air, stable circulation, and good safety performance, and can be applied to solar power generation, wind power generation, smart grid peak shaving, distribution Large-scale energy storage equipment for power stations, backup power sources, or communication base stations.

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Abstract

本发明公开了一种层状含铜氧化物材料及其制备方法和用途，所述材料的化学通式为：Na0.68+aNibCucMdMneO2+δ；其中Ni、Cu、M、Mn分别与最近邻的六个氧原子形成八面体结构并共边排布构成过渡金属层；碱金属离子Na+位于每两层过渡金属层之间；M具体为Mg2+，Mn2+，Zn2+，Co2+，Al3+，B3+，Cr3+，Mn3+，Co3+，V3+，Zr4+，Ti4+，Sn4+，Mo4+，Ru4+，Nb4+，Sb5+，Nb5+，Mo6+，Te6+中的一种或多种；a，b，c，d，e，δ和m满足(0.68+a)+2(b+c)+md+4e＝2(2+δ)且b+c+d+e＝1。

Description

一种层状含铜氧化物材料及其制备方法和用途 技术领域
本发明涉及材料技术领域，尤其涉及一种层状含铜氧化物材料及其制备方法和用途。
背景技术
传统化石能源如煤、石油、天然气等为人类社会提供主要的能源，但随着化石能源的逐渐枯竭，及其带来的日益严重的生态环境恶化等问题，各国都在努力寻找可再生、环境友好的新能源。近来，风能、太阳能等可再生能源得到大力发展，但其间歇性、不稳定性等特点制约了其发展，因此，需要大规模的储能系统实现风电、光电的顺利并网，并用于电网的“削峰填谷”，降低供电成本，提高电网的供电效率、稳定性和可靠性。目前的二次电池主要有镍-氢电池、镍-镉电池、铅酸蓄电池、锂离子电池等。锂离子电池由于体积小、质量轻、比能量高、无记忆效应、无污染、自放电小、循环寿命长而被广泛应用，但是，因为锂资源有限，提取成本高，使得锂离子电池成本升高，无法满足大规模应用的低成本需求，而与其处于同一主族具有相似物理化学性质的钠含量丰富、成本低廉。因此，发展钠离子二次电池作为大规模储能设备再一次引起人们的关注。
近来，钠离子电池电极材料被广泛研究，并有大量钠离子电池正极材料被报道，主要有磷酸盐、氧化物、氟化物、有机化合物等。其中，氟化物动力学性能很差，难以应用；而有机化合物做正极充电到高电压时会发生分解，无法实现高电压，限制了其能量密度。对于磷酸盐正极材料，虽然其聚阴离子对于提高电压有帮助，但由于其质量较大，导致其容量偏低， 限制了在实际中的应用。具有高钠离子电导的NASICON结构是备受关注的一种磷酸盐正极材料，典型的是Na3V2(PO4)3。胡勇胜等首次提出对其进行碳包覆，并对电解液进行优化，3.4V的平台容量达到107mAh/g，显著提高了其循环稳定性【Electrochem.Commun.,2012,14,86-89，Adv.Energy Mater.,2013,3,156-160】。另一种具有代表性的是具有最高平均电压的Na3V2(PO4)2F3,平均电压3.95V，具有120mAh/g的容量【J.Mater.Chem.,2012,22,20535-20541】。尽管Na3V2(PO4)3表现出了优异的性能，但是由于钒资源不够丰富并且五价钒有毒而阻碍了其进一步的发展。
除此之外，氧化物正极材料分为层状和隧道型两种。隧道结构氧化物主要是具有S型大通道的Na0.44MnO2,Cao等人研究了Na0.44MnO2纳米线，以0.5C循环1000周后容量保持率为77％，显示优异的循环性能【Adv.Mater.,2011,23,3155-3160】,但其首周充电只有一半的容量，另一半容量来自于金属钠负极，而实际应用中负极不提供钠，所以其难以应用。层状氧化物根据钠离子所处环境和氧的堆积方式可分为P2相和O3相【Physical B&C,1980,99,81-85】。O3相的电化学循环性能差，而且对于空气和水敏感，难以应用；P2相不仅容量较高，而且由于钠离子所处的空间较大，在电化学循环过程中稳定性好，但是大部分P2相材料在空气中不稳定。2001年，Lu等制备出了P2相的Na2/3Ni1/3Mn2/3O2材料，并对其电化学性能进行了表征，其在2.0V-4.5V之间有160mAh/g的容量【Z.H.Lu and J.R.Dahn,J.Electrochem.Soc.,2001,148,A1225-A1229】，但其电化学曲线表现出多个平台，循环稳定性极差。
发明内容
本发明实施例提供了一种层状含铜氧化物材料及其制备方法和用途。所述层状含铜氧化物材料制备简单，原料资源丰富，成本低廉，是无污染的绿色材料，可以应用于钠离子二次电池正极活性材料，应用本发明的层状 含铜氧化物材料的钠离子二次电池，具有较高的工作电压和首周库仑效率、空气中稳定、循环稳定、安全性能好，可以用于太阳能发电、风力发电、智能电网调峰、分布电站、后备电源或通信基站的大规模储能设备。
第一方面，本发明实施例提供了一种层状含铜氧化物材料，化学通式为：Na0.68+aNibCucMdMneO2+δ；
其中，Ni、Cu、Mn为过渡金属元素，M为对过渡金属位进行掺杂取代的元素；Ni、Cu、Mn和M分别与最近邻的六个氧原子形成八面体结构，多个所述八面体结构共边排布构成过渡金属层；碱金属离子Na+位于每两层所述过渡金属层之间；所述M具体为Mg2+,Mn2+,Zn2+,Co2+,Al3+,B3+,Cr3+,Mn3+,Co3+,V3+,Zr4+，Ti4+,Sn4+，Mo4+,Ru4+，Nb4+,Sb5+,Nb5+,Mo6+，Te6+中的一种或多种；所述M的化合价态为m，所述m具体为一价、二价、三价、四价、五价或六价；所述a，b，c，d，e,δ分别为对应元素所占的摩尔百分比；所述a，b，c，d，e，δ和m之间的关系满足(0.68+a)+2(b+c)+md+4e＝2(2+δ),并且满足b+c+d+e＝1；其中，-0.08≤a≤0.08；0<b≤0.38；0<c<0.38；0≤d<0.36；0<e≤0.7；-0.02<δ<0.02。
优选的，所述层状含铜氧化物材料用于钠离子二次电池的正极活性材料。
在第二方面，本发明实施例提供了一种如上述第一方面所述的层状含铜氧化物材料的制备方法，所述方法为固相法，包括：
将所需钠的化学计量102wt％～108wt％的碳酸钠和所需化学计量的氧化镍、氧化铜、二氧化锰和M的氧化物按比例混合成前驱体；所述M具体为Mg2+,Mn2+,Zn2+,Co2+,Al3+,B3+,Cr3+,Mn3+,Co3+,V3+,Zr4+，Ti4+,Sn4+，Mo4+,Ru4+，Nb4+,Sb5+,Nb5+,Mo6+，Te6+中的一种或多种；
采用球磨的方法将所述前驱体均匀混合得到前驱体粉末；
将所述前驱体粉末置于马弗炉内，在750℃～1000℃的空气气氛中热处理10～24小时；
将热处理后的前驱体粉末进行研磨，得到所述层状含铜氧化物材料。
在第三方面，本发明实施例提供了一种如上述第一方面所述的层状含铜氧化物材料的制备方法，所述方法为喷雾干燥法，包括：
将所需钠的化学计量102wt％～108wt％的碳酸钠和所需化学计量的氧化镍、氧化铜、二氧化锰和M的氧化物按比例混合成前驱体；所述M具体为Mg2+,Mn2+,Zn2+,Co2+,Al3+,B3+,Cr3+,Mn3+,Co3+,V3+,Zr4+，Ti4+,Sn4+，Mo4+,Ru4+，Nb4+,Sb5+,Nb5+,Mo6+，Te6+中的一种或多种；
将所述前驱体加乙醇或水后形成浆料并搅拌均匀；
对所述浆料进行喷雾干燥后得到前驱体粉末；
将所述前驱体粉末置于马弗炉内，在750℃～1000℃的空气气氛中热处理10～24小时；
将热处理后的前驱体粉末进行研磨，得到所述层状含铜氧化物材料。
在第四方面，本发明实施例提供了一种如上述第一方面所述的层状含铜氧化物材料的制备方法，所述方法为溶胶-凝胶法，包括：
将所需钠的化学计量102wt％～108wt％的乙酸钠、所需化学计量的过渡金属的硝酸盐和掺杂元素M的硝酸盐溶于一定体积的去离子水中，在80℃下磁力搅拌，逐渐加入柠檬酸，蒸干形成前驱体凝胶；其中，所述M具体为Mg2+,Mn2+,Zn2+,Co2+,Al3+,B3+,Cr3+,Mn3+,Co3+,V3+,Zr4+，Ti4+,Sn4+，Mo4+,Ru4+，Nb4+,Sb5+,Nb5+,Mo6+，Te6+中的一种或多种；
将所述前驱体凝胶置于坩埚中，在250℃～500℃的空气气氛下，预烧2个小时；
再在750℃～1000℃下热处理5～24小时；
将热处理后的前驱体粉末进行研磨，得到所述层状含铜氧化物材料。
优选的，所述过渡金属包括：Ni、Cu和Mn。
第五方面，本发明实施例提供了一种如上述第二方面、第三方面或第四方面所述的方法制备的层状含铜氧化物材料的用途，所述层状含铜氧化物材料用于太阳能发电、风力发电、智能电网调峰、分布电站、后备电源 或通信基站的大规模储能设备。
第六方面，本发明实施例提供了一种钠离子二次电池的正极极片，所述正极极片包括：
集流体、涂覆于所述集流体之上的导电添加剂和粘结剂和如上述第一方面所述的层状含铜氧化物材料。
第七方面，本发明实施例提供了一种包括上述第六方面所述的正极极片的钠离子二次电池。
第八方面，本发明实施例提供了一种如上述第七方面所述的钠离子二次电池的用途，所述钠离子二次电池用于太阳能发电、风力发电、智能电网调峰、分布电站、后备电源或通信基站的大规模储能设备。
本发明实施例提供的层状含铜氧化物材料制备简单，原料资源丰富，成本低廉，是无污染的绿色材料，可以应用于钠离子二次电池正极活性材料，应用本发明的层状含铜氧化物材料的钠离子二次电池，具有较高的工作电压和首周库仑效率、循环稳定、安全性能好，可以用于太阳能发电、风力发电、智能电网调峰、分布电站、后备电源或通信基站的大规模储能设备。
附图说明
下面通过附图和实施例，对本发明实施例的技术方案做进一步详细描述。
图1为本发明实施例1提供的不同元素摩尔百分比的多个层状含铜氧化物材料的XRD图谱；
图2为本发明实施例2提供的一种层状含铜氧化物材料的制备方法流程图；
图3为本发明实施例3提供的另一种层状含铜氧化物材料的制备方法流程图；
图4为本发明实施例4提供的又一种层状含铜氧化物材料的制备方法流程图；
图5为本发明实施5提供的Na0.68Ni0.23Cu0.11Mn0.66O2的SEM图；
图6为本发明实施例5提供的一种钠离子电池的充放电曲线图；
图7为本发明实施例6提供的一种钠离子电池的充放电曲线图；
图8为本发明实施例7提供的一种钠离子电池的充放电曲线图；
图9为本发明实施例8提供的一种钠离子电池的充放电曲线图；
图10为本发明实施例9提供的一种钠离子电池的充放电曲线图；
图11为本发明实施例10提供的一种钠离子电池的充放电曲线图；
图12为本发明实施例11提供的一种钠离子电池的充放电曲线图；
图13为本发明实施例12提供的一种钠离子电池的充放电曲线图；
图14为本发明实施例13提供的Na0.68Ni0.23Cu0.11Ti0.16Mn0.5O2的SEM图；
图15为本发明实施例13提供的一种钠离子电池的充放电曲线图；
图16为本发明实施例14提供的一种钠离子电池的充放电曲线图。
具体实施方式
下面结合实施例，对本发明进行进一步的详细说明，但并不意于限制本发明的保护范围。
实施例1
本发明实施例1提供了一种层状含铜氧化物材料，其的化学通式为：Na0.68+aNibCucMdMneO2+δ；
其中，Ni、Cu、Mn为过渡金属元素，M为对过渡金属位进行掺杂取代的元素，所述M具体为Mg2+,Mn2+,Zn2+,Co2+,Al3+,B3+,Cr3+,Mn3+,Co3+,V3+,Zr4+，Ti4+,Sn4+，Mo4+,Ru4+，Nb4+,Sb5+,Nb5+,Mo6+，Te6+中的一种或多种；所述M的化合价态为m，所述m具体为一价、二价、三价、四价、五价或者六价；
所述a，b，c，d，e，δ分别为对应元素所占的摩尔百分比；所述a，b，c，d，e，δ和m之间的关系满足(0.68+a)+2(b+c)+md+4e＝2(2+δ),并且满 足b+c+d+e＝1；其中，-0.08≤a≤0.08；0<b≤0.38；0<c<0.38；0≤d<0.36；0<e≤0.7；-0.02<δ<0.02。
在Na0.68+aNibCucMdMneO2+δ的结构中，Ni、Cu、M、Mn分别与最近邻的六个氧原子形成八面体结构，多个八面体结构共边排布构成了过渡金属层，碱金属离子Na+位于每两层过渡金属层之间，从而构成层状结构。
在图1中给出了不同元素摩尔百分比的多个层状含铜氧化物材料的X射线衍射(X-ray diffraction,XRD)图谱，由XRD图谱可以看出，本实施例提供的Na0.68+aNibCucMdMneO2+δ晶体结构为P2相的层状结构的氧化物。
本实施例提供的层状含铜氧化物材料，制备简单，原料资源丰富，成本低廉，是无污染的绿色材料，可以应用于钠离子二次电池的正极活性材料，应用本发明的层状含铜氧化物材料作为正极活性材料的钠离子二次电池，具有较高的工作电压和首周库仑效率、空气中稳定、循环稳定、安全性能好。
实施例2
本实施例提供了一种层状含铜氧化物材料的制备方法，具体为固相法，如图2所示，包括：
步骤201，将所需钠的化学计量102wt％～108wt％的碳酸钠和所需化学计量的氧化镍、氧化铜、二氧化锰和M的氧化物按比例混合成前驱体；
具体的，所述M可以为Mg2+,Mn2+,Zn2+,Co2+,Al3+,B3+,Cr3+,Mn3+,Co3+,V3+,Zr4+，Ti4+,Sn4+，Mo4+,Ru4+，Nb4+,Sb5+,Nb5+,Mo6+，Te6+中的一种或多种。
步骤202，采用球磨的方法将所述前驱体均匀混合得到前驱体粉末；
步骤203，将所述前驱体粉末置于马弗炉内，在750℃～1000℃的空气气氛中热处理10～24小时；
步骤204，将热处理后的前驱体粉末进行研磨，得到所述层状含铜氧化物材料。
本实施例提供的层状含铜氧化物材料的制备方法，能够用于制备上述实施例1中所述的层状含铜氧化物材料。本实施例提供的方法简单易行、成本低廉、适用于可大规模制造的应用。
实施例3
本实施例提供了一种层状含铜氧化物材料的制备方法，具体为喷雾干燥法，如图3所示，包括：
步骤301，将所需钠的化学计量102wt％～108wt％的碳酸钠和所需化学计量的氧化镍、氧化铜、二氧化锰和M的氧化物按比例称量作为前驱体；
具体的，所述M可以为Mg2+,Mn2+,Zn2+,Co2+,Al3+,B3+,Cr3+,Mn3+,Co3+,V3+,Zr4+，Ti4+,Sn4+，Mo4+,Ru4+，Nb4+,Sb5+,Nb5+,Mo6+，Te6+中的一种或多种。
步骤302，将所述前驱体加乙醇或水后搅拌均匀形成浆料；
步骤303，对所述浆料进行喷雾干燥后得到前驱体粉末；
步骤304，将所述前驱体粉末置于马弗炉内，在750℃～1000℃的空气气氛中热处理10～24小时。
步骤305，将热处理后的前驱体粉末进行研磨，得到所述层状含铜氧化物材料。
本实施例提供的层状含铜氧化物材料的制备方法，能够用于制备上述实施例1中所述的层状含铜氧化物材料。本实施例提供的方法简单易行、成本低廉、适用于可大规模制造的应用。
实施例4
本实施例提供了一种层状含铜氧化物材料的制备方法，具体为溶胶-凝胶法，如图4所示，包括：
步骤401，将所需钠的化学计量102wt％～108wt％的乙酸钠、所需化学计量的过渡金属的硝酸盐和掺杂元素M的硝酸盐溶于一定体积的去离子水 中，在80℃下磁力搅拌，并逐渐加入适量的柠檬酸，蒸干形成前驱体凝胶；
其中，过渡金属可以包括：Ni、Cu和Mn。M为对过渡金属位进行掺杂取代的元素，具体为Mg2+,Mn2+,Zn2+,Co2+,Al3+,B3+,Cr3+,Mn3+,Co3+,V3+,Zr4+，Ti4+,Sn4+，Mo4+,Ru4+，Nb4+,Sb5+,Nb5+,Mo6+，Te6+中的一种或多种。
步骤402，将所述前驱体凝胶置于坩埚中，在250℃～500℃的空气气氛下，预烧2个小时；
步骤403，再在750℃～1000℃下热处理5～24小时；
步骤404，将热处理后的前驱体粉末进行研磨，得到所述层状含铜氧化物材料。
本实施例提供的层状含铜氧化物材料的制备方法，能够用于制备上述实施例1中所述的层状含铜氧化物材料。本实施例提供的方法简单易行、成本低廉、适用于可大规模制造的应用。
下述以多个具体实例说明应用本发明实施例2提供的方法制备层状含铜氧化物材料的具体过程，以及将其应用于二次电池的方法和电池特性。
实施例5
本实施例中采用前述实施例2所述的固相法制备层状含铜氧化物材料。
将Na2CO3(分析纯)、NiO(分析纯)、CuO及MnO2按所需化学计量比混合；在玛瑙研钵中研磨半小时，得到前驱体；将前驱体物质转移到Al2O3坩埚内，在马弗炉中900摄氏度下处理15小时，得到黑色粉末的层状含铜氧化物材料Na0.68Ni0.23Cu0.11Mn0.66O2，其XRD图谱参见图1，从XRD图谱上看，Na0.68Ni0.23Cu0.11Mn0.66O2的晶体结构为P2相层状结构的氧化物。图5为Na0.68Ni0.23Cu0.11Mn0.66O2的扫描电子显微镜(SEM)图，从图中可以看出，Na0.68Ni0.23Cu0.11Mn0.66O2的颗粒尺寸分布主要从一微米到五微米，并且伴有一 些棒状颗粒。
将上述制备得到的层状含铜氧化物材料作为电池正极材料的活性物质用于钠离子电池的制备。具体步骤为：将制备好的Na0.68Ni0.23Cu0.11Mn0.66O2粉末与乙炔黑、粘结剂聚偏氟乙烯(PVDF)按照80:10:10的质量比混合，加入适量的N-甲基吡咯烷酮(NMP)溶液，在常温干燥的环境中研磨形成浆料，然后把浆料均匀涂覆于集流体铝箔上，并在红外灯下干燥后，裁成(8×8)mm2的极片。极片在真空条件下，100℃干燥10小时，随即转移到手套箱备用。
模拟电池的装配在Ar气氛的手套箱内进行，以金属钠作为对电极，以NaClO4/碳酸二乙酯(EC:DEC)溶液作为电解液，装配成CR2032扣式电池。使用恒流充放电模式，在C/10电流密度下进行充放电测试。在放电截至电压为2.5V，充电截至电压为4.2V的条件下，测试结果见图6。图6中示出了第一周、第三周和第五周的充放电循环曲线，可以看出，其首周放电比容量可达88.5mAh/g，首周库仑效率约为87.6％，循环非常稳定。
实施例6
本实施例中采用前述实施例2所述的固相法制备层状含铜氧化物材料。
本实施例的具体制备步骤同实施例5，但所用前驱体化合物Na2CO3(分析纯)、NiO(分析纯)、CuO及MnO2的化学计量与实施例5中不同，得到黑色粉末的层状含铜氧化物材料Na0.68Ni0.28Cu0.06Mn0.66O2。
将上述制备得到的层状含铜氧化物材料作为电池正极材料的活性物质用于钠离子电池的制备，并进行电化学充放电测试。其制备过程和测试方法同实施例5。测试电压范围为2.5V～4.2V，测试结果见图7。图7中示出了第一周、第三周及第五周充放电曲线。可以看出，首周放电比容量可达86.4mAh/g，首周库仑效率约为88.4％，并且具有很好的循环稳定性。
实施例7
本实施例中采用前述实施例2所述的固相法制备层状含铜氧化物材料。
本实施例的具体制备步骤同实施例5，但所用前驱体化合物Na2CO3(分析纯)、NiO(分析纯)、CuO、MnO2及MgO的化学计量与实施例5中不同，得到黑色粉末的层状含铜氧化物材料Na0.68Ni0.22Cu0.06Mg0.06Mn0.66O2。
将上述制备得到的层状含铜氧化物材料作为电池正极材料的活性物质用于钠离子电池的制备，并进行电化学充放电测试。其制备过程和测试方法同实施例5。测试电压范围为2.5V～4.2V，测试结果见图8。图8中示出了第一周、第三周及第五周充放电曲线。可以看出，首周放电比容量可达84.3mAh/g，首周库仑效率约为91.3％，并且具有很好的循环稳定性。
实施例8
本实施例中采用前述实施例2所述的固相法制备层状含铜氧化物材料。
本实施例的具体制备步骤同实施例5，但所用前驱体化合物Na2CO3(分析纯)、NiO(分析纯)、CuO、MnO2及ZnO的化学计量与实施例5中不同，得到黑色粉末的层状含铜氧化物材料为Na0.68Ni0.22Cu0.08Zn0.04Mn0.66O2。
将上述制备得到的层状含铜氧化物材料作为电池正极材料的活性物质用于钠离子电池的制备，并进行电化学充放电测试。其制备过程和测试方法同实施例5。测试电压范围为2.5V～4.2V，测试结果见图9。图9中示出了第一周、第三周及第五周充放电曲线。可以看出，首周放电比容量可达91.2mAh/g，首周库仑效率约为89.6％。
实施例9
本实施例中采用前述实施例2所述的固相法制备层状含铜氧化物材 料。
本实施例的具体制备步骤同实施例5，但所用前驱体化合物Na2CO3(分析纯)、NiO(分析纯)、CuO、MnO2及B2O3的化学计量与实施例5中不同，得到黑色粉末的层状含铜氧化物材料为Na0.68Ni0.21Cu0.10B0.06Mn0.63O2。
将上述制备得到的层状含铜氧化物材料作为电池正极材料的活性物质用于钠离子电池的制备，并进行电化学充放电测试。其制备过程和测试方法同实施例5。测试电压范围为2.5V～4.2V，测试结果见图10。图10中示出了第一周、第三周及第五周充放电曲线。可以看出，首周放电比容量可达88.3mAh/g，首周库仑效率约为93.6％，并且具有很好的循环稳定性。
实施例10
本实施例中采用前述实施例2所述的固相法制备的层状含铜氧化物材料。
本实施例的具体制备步骤同实施例5，但所用前驱体化合物Na2CO3(分析纯)、NiO(分析纯)、CuO、MnO2及Al2O3的化学计量与实施例5中不同，得到黑色粉末的层状含铜氧化物材料为Na0.68Ni0.24Cu0.08Al0.04Mn0.64O2。
将上述制备得到的层状含铜氧化物材料作为电池正极材料的活性物质用于钠离子电池的制备，并进行电化学充放电测试。其制备过程和测试方法同实施例5。测试电压范围为2.5V～4.2V，测试结果见图11。图11中示出了第一周、第三周及第五周充放电曲线。可以看出，首周放电比容量可达71.5mAh/g，首周库仑效率约为92.8％，并且具有很好的循环稳定性。
实施例11
本实施例中采用前述实施例2所述的固相法制备层状含铜氧化物材料。
本实施例的具体制备步骤同实施例5，但所用前驱体化合物Na2CO3(分 析纯)、NiO(分析纯)、CuO、MnO2及Co2O3的化学计量与实施例5中不同，得到黑色粉末的层状含铜氧化物材料为Na0.68Ni0.20Cu0.10Co0.08Mn0.62O2，其XRD图谱参见图1。
将上述制备得到的层状含铜氧化物材料作为电池正极材料的活性物质用于钠离子电池的制备，并进行电化学充放电测试。其制备过程和测试方法同实施例5。测试电压范围为2.5V～4.2V，测试结果见图12。图12中示出了第一周、第三周及第五周充放电曲线。可以看出，首周放电比容量可达73mAh/g，首周库仑效率约为85.7％，并且具有很好的循环稳定性。
实施例12
本实施例中采用前述实施例2所述的固相法制备层状含铜氧化物材料。
本实施例的具体制备步骤同实施例5，但所用前驱体化合物Na2CO3(分析纯)、NiO(分析纯)、CuO、MnO2及Fe2O3的化学计量与实施例5中不同，得到黑色粉末的层状含铜氧化物材料为Na0.68Ni0.25Cu0.06Fe0.06Mn0.63O2，其XRD图谱参见图1。
将上述制备得到的层状含铜氧化物材料作为电池正极材料的活性物质用于钠离子电池的制备，并进行电化学充放电测试。其制备过程和测试方法同实施例5。测试电压范围为2.5V～4.2V，测试结果见图13。图13中示出了第一周、第二周及第三周充放电曲线。可以看出，首周放电比容量可达83.5mAh/g，首周库仑效率约为84.6％，并且具有很好的循环稳定性。
实施例13
本实施例中采用前述实施例2所述的固相法制备层状含铜氧化物材料。
本实施例的具体制备步骤同实施例5，但所用前驱体化合物Na2CO3(分 析纯)、NiO(分析纯)、CuO、MnO2及TiO2的化学计量与实施例5中不同，得到黑色粉末的层状含铜氧化物材料为Na0.68Ni0.23Cu0.11Ti0.16Mn0.50O2。
图14为Na0.68Ni0.23Cu0.11Ti0.16Mn0.50O2的扫描电子显微镜(SEM)图，从图中可以看出，Na0.68Ni0.23Cu0.11Ti0.16Mn0.50O2的颗粒尺寸分布主要从几微米到十几微米。
将上述制备得到的层状含铜氧化物材料作为电池正极材料的活性物质用于钠离子电池的制备，并进行电化学充放电测试。其制备过程和测试方法同实施例5。测试电压范围为2.5V～4.2V，测试结果见图15。图15中示出了第一周、第三周及第五周充放电曲线。可以看出，首周放电比容量可达103.2mAh/g，首周库仑效率约为87％，并且具有很好的循环稳定性。
实施例14
本实施例中采用前述实施例2所述的固相法制备层状含铜氧化物材料。
本实施例的具体制备步骤同实施例5，但所用前驱体化合物Na2CO3(分析纯)、NiO(分析纯)、CuO、MnO2及TiO2化学计量比与实施例5不同，得到黑色粉末的层状含铜氧化物材料为Na0.68Ni0.28Cu0.06Ti0.16Mn0.50O2。
将上述制备得到的层状含铜氧化物材料作为电池正极材料的活性物质用于钠离子电池的制备，并进行电化学充放电测试。其制备过程和测试方法同实施例5。测试电压范围为2.5V～4.2V，测试结果见图16。图16中示出了第一周、第二周及第三周充放电曲线。可以看出，首周放电比容量可达106.2mAh/g，首周库仑效率约为84.9％。
实施例15
本实施例中采用前述实施例2所述的固相法制备层状含铜氧化物材料。
本实施例的具体制备步骤同实施例5，但所用前驱体化合物Na2CO3(分析纯)、NiO(分析纯)、CuO、MnO2及Mn2O3化学计量比与实施例5不同，得到黑色粉末的层状含铜氧化物材料为Na0.68Ni0.23Cu0.08Mn0.69O2。
将上述制备得到的层状含铜氧化物材料作为电池正极材料的活性物质用于钠离子电池的制备，并进行电化学充放电测试。其制备过程和测试方法同实施例5。测试电压范围为2.5V～4.2V，结果见下表1。
实施例16
本实施例中采用前述实施例2所述的固相法制备层状含铜氧化物材料。
本实施例的具体制备步骤同实施例5，但所用前驱体化合物Na2CO3(分析纯)、NiO(分析纯)、CuO、MnO2及V2O3化学计量比与实施例5不同，得到黑色粉末的层状含铜氧化物材料为Na0.68Ni0.22Cu0.08V0.08Mn0.62O2。
将上述制备得到的层状含铜氧化物材料作为电池正极材料的活性物质用于钠离子电池的制备，并进行电化学充放电测试。其制备过程和测试方法同实施例5。测试电压范围为2.5V～4.2V，结果见下表1。
实施例17
本实施例中采用前述实施例2所述的固相法制备层状含铜氧化物材料。
本实施例的具体制备步骤同实施例5，但所用前驱体化合物Na2CO3(分析纯)、NiO(分析纯)、CuO、MnO2及SnO2化学计量比与实施例5不同，得到黑色粉末的层状含铜氧化物材料为Na0.68Ni0.24Cu0.10Mn0.54Sn0.12O2。
将上述制备得到的层状含铜氧化物材料作为电池正极材料的活性物质用于钠离子电池的制备，并进行电化学充放电测试。其制备过程和测试方法同实施例5。测试电压范围为2.5V～4.2V，结果见下表1。
实施例18
本实施例中采用前述实施例2所述的固相法制备层状含铜氧化物材料。
本实施例的具体制备步骤同实施例5，但所用前驱体化合物Na2CO3(分析纯)、NiO(分析纯)、CuO、MnO2及Nb2O5化学计量比与实施例5不同，得到黑色粉末的层状含铜氧化物材料为Na0.68Ni0.26Cu0.10Mn0.60Nb0.04O2。
将上述制备得到的层状含铜氧化物材料作为电池正极材料的活性物质用于钠离子电池的制备，并进行电化学充放电测试。其制备过程和测试方法同实施例5。测试电压范围为2.5V～4.2V，结果见下表1。
实施例19
本实施例中采用前述实施例2所述的固相法制备层状含铜氧化物材料。
本实施例的具体制备步骤同实施例5，但所用前驱体化合物Na2CO3(分析纯)、NiO(分析纯)、CuO及MnO2化学计量比与实施例5不同，得到黑色粉末的层状含铜氧化物材料为Na0.72Ni0.24Cu0.12Mn0.64O2。
将上述制备得到的层状含铜氧化物材料作为电池正极材料的活性物质用于钠离子电池的制备，并进行电化学充放电测试。其制备过程和测试方法同实施例5。测试电压范围为2.5V～4.2V，结果见下表1。
实施例20
本实施例中采用前述实施例2所述的固相法制备层状含铜氧化物材料。
本实施例的具体制备步骤同实施例5，但所用前驱体化合物Na2CO3(分析纯)、NiO(分析纯)、CuO、MnO2及MgO化学计量比与实施例5不同，得 到黑色粉末的层状含铜氧化物材料为Na0.70Ni0.22Cu0.08Mg0.05Mn0.65O2。
将上述制备得到的层状含铜氧化物材料作为电池正极材料的活性物质用于钠离子电池的制备，并进行电化学充放电测试。其制备过程和测试方法同实施例5。测试电压范围为2.5V～4.2V，结果见下表1。
Figure PCTCN2015081802-appb-000001
表1
虽然上述实施例5-20以应用本发明实施例2提供的方法来说明制备层状含铜氧化物材料的具体过程，以及将其应用于二次电池的方法和电池特性，但并不限定上述实施例5-20只能应用本发明实施例2提供的固相法来进行材料制备，本领域技术人员容易想到，还可采用本发明实施例3提供的喷雾干燥法或实施例4提供的溶胶-凝胶法来制备获得上述实施例5-20的层状含铜氧化物材料。
本发明上述实施例中提供的层状含铜氧化物材料制备简单，原料资源丰富，成本低廉，是无污染的绿色材料，可以作为钠离子二次电池的正极活性材料应用于钠离子二次电池中，这样制备获得的钠离子二次电池，具有较高的工作电压和首周库仑效率、空气中稳定、循环稳定、安全性能好，可以应用于太阳能发电、风力发电、智能电网调峰、分布电站、后备电源或通信基站的大规模储能设备。
以上所述的具体实施方式，对本发明的目的、技术方案和有益效果进行了进一步详细说明，所应理解的是，以上所述仅为本发明的具体实施方式而已，并不用于限定本发明的保护范围，凡在本发明的精神和原则之内，所做的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。

Claims (10)

  1. 一种层状含铜氧化物材料，其特征在于，所述层状含铜氧化物材料的化学通式为：Na0.68+aNibCucMdMneO2+δ；
    其中，Ni、Cu、Mn为过渡金属元素，M为对过渡金属位进行掺杂取代的元素；Ni、Cu、Mn和M分别与最近邻的六个氧原子形成八面体结构，多个所述八面体结构共边排布构成过渡金属层；碱金属离子Na+位于每两层所述过渡金属层之间；所述M具体为Mg2+,Mn2+,Zn2+,Co2+,Al3+,B3+,Cr3+,Mn3+,Co3+,V3+,Zr4+，Ti4+,Sn4+，Mo4+,Ru4+，Nb4+,Sb5+,Nb5+,Mo6+，Te6+中的一种或多种；所述M的化合价态为m，所述m具体为一价、二价、三价、四价、五价或六价；所述a，b，c，d，e,δ分别为对应元素所占的摩尔百分比；所述a，b，c，d，e，δ和m之间的关系满足(0.68+a)+2(b+c)+md+4e＝2(2+δ),并且满足b+c+d+e＝1；其中，-0.08≤a≤0.08；0<b≤0.38；0<c<0.38；0≤d<0.36；0<e≤0.7；-0.02<δ<0.02。
  2. 根据权利要求1所述的层状含铜氧化物材料，其特征在于，所述层状含铜氧化物材料用于钠离子二次电池的正极活性材料。
  3. 一种如上述权利要求1所述的层状含铜氧化物材料的制备方法，其特征在于，所述方法为固相法，包括：
    将所需钠的化学计量102wt％～108wt％的碳酸钠和所需化学计量的氧化镍、氧化铜、二氧化锰和M的氧化物按比例混合成前驱体；所述M具体为Mg2+,Mn2+,Zn2+,Co2+,Al3+,B3+,Cr3+,Mn3+,Co3+,V3+,Zr4+，Ti4+,Sn4+，Mo4+,Ru4+，Nb4+,Sb5+,Nb5+,Mo6+，Te6+中的一种或多种；
    采用球磨的方法将所述前驱体均匀混合得到前驱体粉末；
    将所述前驱体粉末置于马弗炉内，在750℃～1000℃的空气气氛中热处理10～24小时；
    将热处理后的前驱体粉末进行研磨，得到所述层状含铜氧化物材料。
  4. 一种如上述权利要求1所述的层状含铜氧化物材料的制备方法， 其特征在于，所述方法为喷雾干燥法，包括：
    将所需钠的化学计量102wt％～108wt％的碳酸钠和所需化学计量的氧化镍、氧化铜、二氧化锰和M的氧化物按比例混合成前驱体；所述M具体为Mg2+,Mn2+,Zn2+,Co2+,Al3+,B3+,Cr3+,Mn3+,Co3+,V3+,Zr4+，Ti4+,Sn4+，Mo4+,Ru4+，Nb4+,Sb5+,Nb5+,Mo6+，Te6+中的一种或多种；
    将所述前驱体加乙醇或水后形成浆料并搅拌均匀；
    对所述浆料进行喷雾干燥后得到前驱体粉末；
    将所述前驱体粉末置于马弗炉内，在750℃～1000℃的空气气氛中热处理10～24小时；
    将热处理后的前驱体粉末进行研磨，得到所述层状含铜氧化物材料。
  5. 一种如上述权利要求1所述的层状含铜氧化物材料的制备方法，其特征在于，所述方法为溶胶-凝胶法，包括：
    将所需钠的化学计量102wt％～108wt％的乙酸钠、所需化学计量的过渡金属的硝酸盐和掺杂元素M的硝酸盐溶于一定体积的去离子水中，在80℃下磁力搅拌，逐渐加入柠檬酸，蒸干形成前驱体凝胶；其中，所述M具体为Mg2+,Mn2+,Zn2+,Co2+,Al3+,B3+,Cr3+,Mn3+,Co3+,V3+,Zr4+，Ti4+,Sn4+，Mo4+,Ru4+，Nb4+,Sb5+,Nb5+,Mo6+，Te6+中的一种或多种；
    将所述前驱体凝胶置于坩埚中，在250℃～500℃的空气气氛下，预烧2个小时；
    再在750℃～1000℃下热处理5～24小时；
    将热处理后的前驱体粉末进行研磨，得到所述层状含铜氧化物材料。
  6. 根据权利要求5所述的方法，其特征在于，所述过渡金属包括：Ni、Cu和Mn。
  7. 一种如上述权利要求3-6任一权项所述的方法制备的层状含铜氧化物材料的用途，其特征在于，所述层状含铜氧化物材料用于太阳能发电、风力发电、智能电网调峰、分布电站、后备电源或通信基站的大规模储能 设备。
  8. 一种钠离子二次电池的正极极片，其特征在于，所述正极极片包括：
    集流体、涂覆于所述集流体之上的导电添加剂和粘结剂和如上述权利要求1所述的层状含铜氧化物材料。
  9. 一种包括上述权利要求8所述的正极极片的钠离子二次电池。
  10. 一种如上述权利要求9所述的钠离子二次电池的用途，其特征在于，所述钠离子二次电池用于太阳能发电、风力发电、智能电网调峰、分布电站、后备电源或通信基站的大规模储能设备。
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