WO2016058402A1 - 一种层状氧化物材料、制备方法、极片、二次电池和用途 - Google Patents

一种层状氧化物材料、制备方法、极片、二次电池和用途 Download PDF

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WO2016058402A1
WO2016058402A1 PCT/CN2015/081816 CN2015081816W WO2016058402A1 WO 2016058402 A1 WO2016058402 A1 WO 2016058402A1 CN 2015081816 W CN2015081816 W CN 2015081816W WO 2016058402 A1 WO2016058402 A1 WO 2016058402A1
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oxide material
layered oxide
precursor
sodium
layered
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French (fr)
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胡勇胜
穆林沁
陈立泉
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中国科学院物理研究所
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Priority to EP15837166.6A priority Critical patent/EP3048659B1/en
Priority to US14/913,389 priority patent/US9728780B2/en
Priority to JP2016520599A priority patent/JP6501766B2/ja
Priority to KR1020177013099A priority patent/KR20170070180A/ko
Publication of WO2016058402A1 publication Critical patent/WO2016058402A1/zh

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    • C01G53/50—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese of the type [MnO2]n-, e.g. Li(NixMn1-x)O2, Li(MyNixMn1-x-y)O2
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    • 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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    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the invention relates to the technical field of materials, in particular to a layered oxide material, a preparation method, a pole piece, a secondary battery and a use.
  • the existing electrochemical energy storage devices mainly include lead-acid batteries, zinc-nickel batteries, hydrogen-nickel batteries, flow batteries, and lithium ion batteries.
  • lithium ion secondary batteries mostly use lithium ion intercalation compounds as positive and negative materials, and dry organic solvents as electrolytes; lithium ions reversibly deintercalate between positive and negative active materials without damaging the structure of the materials. .
  • Lithium-ion battery is three times more cadmium-nickel and hydrogen-nickel battery due to its high working voltage (3.6V); it is small in size, 30% smaller than hydrogen-nickel battery; lighter in weight, 50% lighter than hydrogen-nickel battery; High energy (200Wh/kg), 2-3 times that of cadmium-nickel battery; no memory effect, no pollution, low self-discharge, long cycle life, and become the most promising power battery and renewable energy for electric vehicles. Energy storage battery.
  • the positive electrode material mainly includes Na 3 V 2 (PO 4 ) 3 of NASCION structure [Electrochem.Commun., 2012, 14, 86-89, Adv. Energy Mater ., 2013, 3 , 156-160], NaVPO 4 , Na 3 V 2 (PO 4 ) 3 F 3 [J. Mater.
  • Hot layered cathode material is also in recent years, all research, P2 of the phase of Na x TMO 2 NaTMO 2 and O3 phase is the most studied material [Phys ica l B & C, 1980,99,81-85], sodium O3 phase
  • the content is high, the charging capacity is high in the first week, but its electrochemical cycle performance is poor, and it is sensitive to air and water, and it is difficult to apply; the P2 phase is stable in the electrochemical cycle due to the large space of sodium ions.
  • the deintercalation of sodium ions is faster, but most P2 phase materials are unstable in air and their charge capacity is generally lower in the first week due to lower sodium content.
  • the existing layered oxides must have high charging capacity, high efficiency, good rate performance and good cycleability in the first week, and must contain nickel or cobalt as a variable element.
  • the compounds of these two elements are costly, toxic and environmentally unfriendly.
  • Embodiments of the present invention provide a layered oxide material, a preparation method, a pole piece, a secondary battery, and use.
  • the layered oxide material is simple to prepare, and contains transition metals such as copper, iron and manganese.
  • the non-toxic and safe element has a high abundance in the earth's crust and is therefore inexpensive to manufacture.
  • the sodium ion secondary battery using the layered oxide material of the invention has high efficiency, excellent cycle performance, good safety performance and great practical value, and can be used for solar power generation, wind power generation, smart grid peak shaving and 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 oxide material having a chemical formula of: Na x Cu i Fe j Mn k M y O 2+ ⁇ ;
  • M is an element for doping substitution of a transition metal site, specifically Li + , Ni 2+ , Mg 2+ , Mn 2+ , Zn 2+ , Co 2+ , Ca 2+ , Ba 2+ , Sr 2 + , Mn 3+ , Al 3+ , B 3+ , Cr 3+ , Co 3+ , V 3+ , Zr 4+ , Ti 4+ , Sn 4+ , V 4+ , Mo 4+ , Mo 5+ , One or more of Ru 4+ , Nb 5+ , Si 4+ , Sb 5+ , Nb 5+ , Mo 6+ , Te 6+ ;
  • the space group of the layered oxide material is R3m.
  • the layered 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 oxide material according to the above first aspect, which is a solid phase method, comprising:
  • the stoichiometric sodium salt of 100% to 108% by weight of the desired sodium and the desired stoichiometric amount of oxides of copper oxide, iron oxide, manganese oxide and M are mixed in proportion to form a precursor;
  • the M is specifically Li + , Ni 2+ , Mg 2+ , Mn 2+ , Zn 2+ , Co 2+ , Ca 2+ , Ba 2+ , Sr 2+ , Mn 3+ , Al 3+ , B 3+ , Cr 3+ , Co 3+ , V 3+ , Zr 4+ , Ti 4+ , Sn 4+ , V 4+ , Mo 4+ , Mo 5+ , Ru 4+ , Nb 5+ , Si 4+ , Sb 5+ , Nb 5+ , Mo One or more of 6+ and Te 6+ ;
  • 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 700 ° C to 1000 ° C for 2 to 24 hours;
  • the heat-treated precursor powder is ground to obtain the layered oxide material.
  • the embodiment of the present invention provides the layered oxidation according to the first aspect described above.
  • a method of preparing a material the method being a spray drying method, comprising:
  • the stoichiometric sodium salt of 100% to 108% by weight of the desired sodium and the desired stoichiometric amount of oxides of copper oxide, iron oxide, manganese oxide and M are mixed in proportion to form a precursor;
  • the M is specifically Li + , Ni 2+ , Mg 2+ , Mn 2+ , Zn 2+ , Co 2+ , Ca 2+ , Ba 2+ , Sr 2+ , Mn 3+ , Al 3+ , B 3+ , Cr 3+ , Co 3+ , V 3+ , Zr 4+ , Ti 4+ , Sn 4+ , V 4+ , Mo 4+ , Mo 5+ , Ru 4+ , Nb 5+ , Si 4+ , Sb 5+ , Nb 5+ , Mo One or more of 6+ and Te 6+ ;
  • the precursor is added with ethanol or water and stirred to form a slurry;
  • the precursor powder is placed in a muffle furnace and heat treated in an air atmosphere of 650 ° C to 1000 ° C for 2 to 24 hours;
  • the heat-treated precursor powder is ground to obtain the layered oxide material.
  • the embodiment of the present invention provides a method for preparing a layered oxide material according to the above first aspect, which is a spray drying method, comprising:
  • the stoichiometric ratio of sodium nitrate, copper nitrate, iron nitrate, manganese acetate and M nitrate is used as a precursor;
  • the M is specifically Li + , Ni 2+ , Mg 2+ , Mn 2+ , Zn 2+ , Co 2+ , Ca 2+ , Ba 2+ , Sr 2+ , Mn 3+ , Al 3+ , B 3+ , Cr 3+ , Co 3+ , V 3+ , Zr 4+ , Ti 4+ , Sn 4+
  • the precursor powder is placed in a muffle furnace and heat-treated in an air atmosphere at 650 ° C ⁇ 1000 ° C for 2 to 24 hours;
  • the heat-treated precursor powder is ground to obtain the layered oxide material.
  • the present invention provides a method for preparing a layered oxide material according to the above first aspect, which is a sol-gel method, comprising:
  • the M is specifically Li + , Ni 2+ , Mg 2+ , Mn 2+ , Zn 2+ , Co 2+ , Ca 2+ , Ba 2+ , Sr 2+ , Mn 3+ , Al 3+ , B 3+ , Cr 3+ , Co 3+ , V 3+ , Zr 4+ , Ti 4+ , Sn 4+ , V 4+ , Mo 4+ , Ru 4+ , Mo 5+ , one or more of Nb 5+ , Si 4+ , Sb 5+ , Nb 5+ , Mo 6+ , Te 6+ ;
  • the precursor gel is placed in a crucible, and calcined in an air atmosphere at 200 to 500 ° C for 2 hours;
  • the heat-treated precursor powder is ground to obtain the layered oxide material.
  • the embodiment of the present invention provides a method for preparing a layered oxide material according to the above first aspect, wherein the method is a coprecipitation method, comprising:
  • the solution is slowly added dropwise to a certain concentration and pH of the aqueous ammonia solution to form a precipitate;
  • the obtained precipitate is washed with deionized water, dried and then uniformly mixed with sodium carbonate in a stoichiometric ratio to obtain a precursor;
  • the precursor is placed in a crucible, and heat treated in an air atmosphere at 600 ° C to 1000 ° C for 6 to 24 hours to obtain a precursor powder;
  • the heat-treated precursor powder is ground to obtain the layered oxide material.
  • 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 seventh aspect.
  • the embodiment of the present invention provides the use of the sodium ion secondary battery according to the eighth aspect, wherein the sodium ion secondary battery is used for solar power generation, wind power generation, and smart electricity.
  • the sodium ion secondary battery is used for solar power generation, wind power generation, and smart electricity.
  • Large-scale energy storage equipment for network peaking, distribution power stations, backup power sources or communication base stations.
  • the layered oxide material provided by the embodiment of the invention is simple to prepare, and the transition metal copper, iron and manganese contained therein are all non-toxic and safe elements, and the abundance in the earth's crust is high, so the manufacturing cost is low.
  • a sodium ion secondary battery using the layered oxide material of the present invention depending on a bivalent to trivalent copper transition, a trivalent to tetravalent iron transition and a trivalent to tetravalent manganese price change to achieve a relatively high first week charging capacity It has excellent cycle performance, good safety performance and great practical value. It can be used for large-scale energy storage equipment of solar power generation, wind power generation, smart grid peak shaving, distributed power station, backup power supply or communication base station.
  • Example 1 is an XRD pattern of a plurality of layered 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 oxide material prepared by a solid phase method according to Embodiment 2 of the present invention
  • FIG. 3 is a flow chart of a method for preparing a layered oxide material by a spray drying method according to Embodiment 3 of the present invention
  • FIG. 4 is a flow chart showing a preparation method of a layered copper-containing oxide material prepared by a sol-gel method according to Embodiment 4 of the present invention
  • FIG. 5 is a flow chart of a preparation method for preparing a layered copper-containing oxide material by a coprecipitation method according to Embodiment 5 of the present invention
  • FIG. 6 is a graph showing charge and discharge curves of a sodium ion battery according to Embodiment 6 of the present invention.
  • Figure 7 is a SEM image of NaCu 0.15 Fe 0.4 Mn 0.35 Ni 0.1 O 2 provided in Example 7 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 15 is a SEM image of Na 0.9 Cu 0.225 Fe 0.3 Mn 0.425 Al 0.05 O 2 provided in Example 14 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.
  • FIG. 17 is a graph showing charge and discharge curves of a sodium ion battery according to Embodiment 15 of the present invention.
  • Embodiment 19 is a graph showing charge and discharge curves of a sodium ion battery according to Embodiment 17 of the present invention.
  • Figure 21 is an SEM image of Na 0.9 Cu 0.225 Fe 0.3 Mn 0.475 O 2 provided in Example 19 of the present invention.
  • Figure 23 is a SEM image of Na 0.9 Cu 0.225 Fe 0.3 Mn 0.475 O 2 provided in Example 20 of the present invention.
  • Figure 25 is a graph showing charge and discharge curves of a sodium ion battery according to Embodiment 21 of the present invention.
  • Figure 26 is a graph showing charge and discharge curves of a sodium ion battery according to Embodiment 26 of the present invention.
  • Figure 27 is a graph showing charge and discharge curves of a sodium ion battery according to Embodiment 26 of the present invention.
  • Embodiment 1 of the present invention provides a layered oxide material having a chemical formula of: Na x Cu i Fe j Mn k M y O 2+ ⁇ ;
  • M is an element for doping substitution of a transition metal site, specifically Li + , Ni 2+ , Mg 2+ , Mn 2+ , Zn 2+ , Co 2+ , Ca 2+ , Ba 2+ , Sr 2 + , Mn 3+ , Al 3+ , B 3+ , Cr 3+ , Co 3+ , V 3+ , Zr 4+ , Ti 4+ , Sn 4+ , V 4+ , Mo 4+ , Mo 5+ , One or more of Ru 4+ , Nb 5+ , Si 4+ , Sb 5+ , Nb 5+ , Mo 6+ , Te 6+ ;
  • the space group of the layered oxide material is R3m.
  • FIG. 1 An X-ray diffraction (XRD) pattern of a plurality of layered oxide materials with different element mole percentages is given in FIG. 1. It can be seen from the XRD pattern that the Na x Cu i provided in this embodiment The crystal structure of Fe j Mn k M y O 2+ ⁇ is an oxide of a layered structure of the O 3 phase.
  • the layered oxide material provided in this embodiment is simple to prepare, and the transition metal copper, iron and manganese contained therein are all non-toxic and safe materials, and have high richness in the earth's crust, so the manufacturing cost is low. It can be applied to a positive electrode active material of a sodium ion secondary battery.
  • a sodium ion secondary battery using the layered oxide material of the present invention depending on a bivalent to trivalent copper transition, a trivalent to tetravalent iron transition and a trivalent to tetravalent manganese price change to achieve a relatively high first week charging capacity Excellent cycle performance, good safety performance and great practical value.
  • This embodiment provides a method for preparing a layered oxide material, specifically a solid phase method, as shown in FIG. 2, comprising:
  • Step 201 mixing stoichiometric amounts of 100% by weight to 108% by weight of the sodium required sodium carbonate and the desired stoichiometric amounts of oxides of copper oxide, iron oxide, manganese oxide and M to form a precursor;
  • the M is specifically Li + , Ni 2+ , Mg 2+ , Mn 2+ , Zn 2+ , Co 2+ , Ca 2+ , Ba 2+ , Sr 2+ , Mn 3+ , Al 3+ , B 3+ , Cr 3+ , Co 3+ , V 3+ , Zr 4+ , Ti 4+ , Sn 4+ , V 4+ , Mo 4+ , Mo 5+ , Ru 4+ , Nb 5+ , Si One or more of 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 placing the precursor powder in a muffle furnace, air at 700 ° C to 1000 ° C Heat treatment in the atmosphere for 2 to 24 hours;
  • step 204 the heat-treated precursor powder is ground to obtain the layered oxide material.
  • the method for preparing the layered oxide material provided in this embodiment can be used to prepare the layered oxide material described in the above embodiment 1.
  • the method provided by the embodiment is simple and easy to operate, low in cost, safe and non-toxic, and suitable for large-scale manufacturing applications.
  • This embodiment provides a method for preparing a layered oxide material, specifically a spray drying method, as shown in FIG. 3, comprising:
  • Step 301 mixing stoichiometric amounts of 100% by weight to 108% by weight of sodium sodium and oxides of copper oxide, iron oxide, manganese oxide and M into a precursor; or using a stoichiometric ratio of sodium nitrate, Copper nitrate, ferric nitrate, manganese acetate and M nitrate are precursors;
  • the M may be Li + , Ni 2+ , Mg 2+ , Mn 2+ , Zn 2+ , Co 2+ , Ca 2+ , Ba 2+ , Sr 2+ , Mn 3+ , Al 3+ , B 3+ , Cr 3+ , Co 3+ , V 3+ , Zr 4+ , Ti 4+ , Sn 4+ , V 4+ , Mo 4+ , Mo 5+ , Ru 4+ , Nb 5+ , Si One or more of 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, heat treatment in an air atmosphere of 650 ° C ⁇ 1000 ° C for 2 to 24 hours;
  • step 305 the heat-treated precursor powder is ground to obtain the layered oxide material.
  • the method for preparing the layered oxide material provided in this embodiment can be used to prepare the layered oxide material described in the above embodiment 1.
  • the method provided by the embodiment is simple and easy to operate, low in cost, safe and non-toxic, and suitable for large-scale manufacturing applications.
  • This embodiment provides a method for preparing a layered oxide material, specifically a sol-gel method, as shown in FIG. 4, comprising:
  • Step 401 stoichiometrically dissolving 100% by weight to 108% by weight of sodium or sodium nitrate or sodium carbonate or sodium sulfate, and a nitrate or sulfate containing copper, iron, manganese, and doping element M. Mixing in water or dissolved in ethanol to form a precursor solution;
  • the M is specifically Li + , Ni 2+ , Mg 2+ , Mn 2+ , Zn 2+ , Co 2+ , Ca 2+ , Ba 2+ , Sr 2+ , Mn 3+ , Al 3+ , B 3+ , Cr 3+ , Co 3+ , V 3+ , Zr 4+ , Ti 4+ , Sn 4+ , V 4+ , Mo 4+ , Ru 4+ , Mo 5+ , Nb 5+ , Si 4 + , one or more of Sb 5+ , Nb 5+ , Mo 6+ , Te 6+ .
  • Step 402 stirring at 50 ° C ⁇ 100 ° C, and adding an appropriate amount of chelating agent, evaporation to dryness to form a precursor gel;
  • Step 403 the precursor gel is placed in a crucible, and pre-fired for 2 hours in an air atmosphere of 200 ° C to 500 ° C;
  • Step 404 further heat treatment at 600 ° C ⁇ 1000 ° C for 2 to 24 hours;
  • step 405 the heat-treated precursor powder is ground to obtain the layered oxide material.
  • the method for preparing the layered oxide material provided in this embodiment can be used to prepare the layered oxide material described in the above embodiment 1.
  • the method provided by the embodiment is simple and easy to operate, low in cost, safe and non-toxic, and suitable for large-scale manufacturing applications.
  • This embodiment provides a method for preparing a layered oxide material, specifically a coprecipitation method, as shown in FIG. 5, comprising:
  • Step 501 dissolving a desired stoichiometric ratio of a nitrate or a sulfate or a carbonate or a hydroxide containing copper, iron, manganese and M in a volume of deionized water, respectively, and forming a solution;
  • the M is specifically Li + , Ni 2+ , Mg 2+ , Mn 2+ , Zn 2+ , Co 2+ , Ca 2+ , Ba 2+ , Sr 2+ , Mn 3+ , Al 3+ , B 3+ , Cr 3+ , Co 3+ , V 3+ , Zr 4+ , Ti 4+ , Sn 4+ , V 4+ , Mo 4+ , Ru 4+ , Mo 5+ , Nb 5+ , Si 4 + , one or more of Sb 5+ , Nb 5+ , Mo 6+ , Te 6+ .
  • Step 502 using a peristaltic pump to slowly add the solution to a certain concentration and pH of the aqueous ammonia solution to form a precipitate;
  • Step 503 the obtained precipitate is washed with deionized water, dried and then uniformly mixed with sodium carbonate in a stoichiometric ratio to obtain a precursor;
  • Step 504 placing the precursor in a crucible, and heat-treating in an air atmosphere at 600 ° C to 1000 ° C for 2 to 24 hours to obtain a precursor powder;
  • step 505 the heat-treated precursor powder is ground to obtain the layered oxide material.
  • the method for preparing the layered oxide material provided in this embodiment can be used to prepare the layered oxide material described in the above embodiment 1.
  • the method provided by the embodiment is simple and easy to operate, low in cost, safe and non-toxic, and suitable for large-scale manufacturing applications.
  • the layered oxide material is prepared by the solid phase method described in the foregoing embodiment 2, including:
  • Na 2 CO 3 (analytical grade), Fe 2 O 3 (analytical grade), CuO, Mn 2 O 3 were mixed in a desired stoichiometric ratio; ground in an agate mortar for half an hour to obtain a precursor; the precursor was pressed
  • the sheet was transferred to Al 2 O 3 crucible and treated in a muffle furnace at 850 ° C for 12 hours to obtain a black powdered layered oxide material NaCu 0.2 Fe 0.4 Mn 0.4 O 2 .
  • the XRD pattern thereof is shown in Fig. 1, from XRD.
  • the crystal structure of NaCu 0.2 Fe 0.4 Mn 0.4 O 2 is an oxide of a layered structure of O3 phase.
  • the layered oxide material prepared above is used as an active material of a battery cathode material for the preparation of a sodium ion battery, and the specific steps are as follows: preparing the prepared NaCu 0.2 Fe 0.4 Mn 0.4 O 2 powder with acetylene black and a binder.
  • the vinylidene fluoride (PVDF) is mixed in a mass ratio of 80:10:10, and an appropriate amount of N-methylpyrrolidone (NMP) solution is added, and the slurry is ground in a dry environment at normal temperature, and then the slurry is uniformly coated on the set.
  • PVDF vinylidene fluoride
  • NMP N-methylpyrrolidone
  • a pole piece of (8 x 8) mm 2 was cut. The pole piece was dried under vacuum at 110 ° 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. The test results are shown in Fig. 6 under the condition that the discharge cut-off voltage is 2.5V and the charge cut-off voltage is 4.1V.
  • the charge and discharge cycle curves of the first week and the second week are shown in Fig. 6. It can be seen that the first cycle discharge specific capacity is up to 90.4 mAh/g, and the first week coulombic efficiency is about 82.3%, and the cycle is very stable.
  • the layered oxide material is prepared by the solid phase method described in the foregoing embodiment 2.
  • Example 6 The specific preparation steps of the examples are the same as those in Example 6, but the stoichiometry and implementation of the precursor compounds Na 2 CO 3 (analytical grade), NiO (analytical grade), Fe 2 O 3 , CuO, Mn 2 O 3 , MnO 2 used .
  • the heat treatment conditions were 950 ° C for 10 hours, and the layered oxide material obtained as a black powder was NaCu 0.15 Fe 0.4 Mn 0.35 Ni 0.1 O 2 , and the XRD pattern thereof is shown in Fig. 1 .
  • Figure 7 is a scanning electron microscope (SEM) image of NaCu 0.15 Fe 0.4 Mn 0.35 Ni 0.1 O 2 .
  • the particle size distribution of the material is mainly from 1 ⁇ m to 10 ⁇ m.
  • the layered 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 6.
  • the test voltage range is from 2.5V to 4.0V, and the test results are shown in Figure 8.
  • Figure 8 shows Charge and discharge curves for the first and second weeks. It can be seen that the first week discharge specific capacity can reach 105.3mAh/g, and the first week coulombic efficiency is about 93.8%.
  • the layered oxide material is prepared by the solid phase method described in the foregoing embodiment 2.
  • Example 6 The specific preparation procedure of this example is the same as that of Example 6, but the stoichiometry of the precursor compounds Na 2 CO 3 (analytical grade), Fe 2 O 3 , CuO, MnO 2 and TiO 2 used is different from that in Example 6, and black is obtained.
  • the layered oxide material of the powder was NaCu 0.1 Fe 0.5 Mn 0.3 Ti 0.1 O 2 , and its XRD pattern is shown in Fig. 1.
  • the layered 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 6.
  • the test voltage range is 2.5V to 4.0V, and the test results are shown in Figure 9.
  • the first and second week charge and discharge curves are shown in FIG. It can be seen that the first week discharge specific capacity can reach 97.6 mAh / g, the first week Coulomb efficiency is about 89.7%.
  • the layered oxide material is prepared by the solid phase method described in the foregoing embodiment 2.
  • the specific preparation procedure of the present embodiment is the same as that of Example 6, but the stoichiometry of the precursor compounds Na 2 CO 3 (analytical grade), Fe 2 O 3 , CuO, Mn 2 O 3 and TiO 2 used is the same as in Example 6.
  • the layered oxide material obtained as a black powder was NaCu 0.2 Fe 0.4 Mn 0.3 Ti 0.1 O 2 , and its XRD pattern was similar to that of FIG.
  • the layered 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 6.
  • the test voltage range is 2.5V to 4.0V, and the test results are shown in Figure 10.
  • the first and second weeks of charge and discharge curves are shown in FIG. It can be seen that the first week discharge specific capacity can reach 90.1 mAh / g, the first week Coulomb efficiency is about 88%.
  • the layered oxide material prepared by the solid phase method described in the foregoing embodiment 2 is used.
  • Example 6 The specific preparation steps of this example are the same as those of Example 6, but the stoichiometry of the precursor compounds Na 2 CO 3 (analytical grade), Fe 2 O 3 , CuO, Mn 2 O 3 and MnO 2 used is different from that in Example 6.
  • the layered oxide material obtained as a black powder was Na 0.9 Cu 0.225 Fe 0.3 Mn 0.475 O 2 , and its XRD pattern was similar to that of FIG.
  • the layered 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 6.
  • the test voltage range is from 2.5V to 4.1V, and the test results are shown in Figure 11.
  • the first and second weeks of charge and discharge curves are shown in FIG. It can be seen that the first week discharge specific capacity can reach 101.4 mAh / g, the first week Coulomb efficiency is about 89.8%.
  • the layered 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 6, except that the stoichiometric amounts of the precursor compounds Na 2 CO 3 (analytical grade), Fe 2 O 3 , CuO and Mn 2 O 3 are different from those in Example 6, and a black powder is obtained.
  • the layered oxide material is Na 0.833 Cu 0.167 Fe 0.333 Mn 0.5 O 2 , and its XRD pattern is shown in FIG.
  • the layered 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 6.
  • the test voltage range is 2.5V to 4.1V, and the test results are shown in Figure 12.
  • the first and second weeks of charge and discharge curves are shown in FIG. It can be seen that the first week discharge specific capacity can reach 86.2 mAh / g, the first week Coulomb efficiency is about 85.7%.
  • the layered oxide material is prepared by the solid phase method described in the foregoing embodiment 2.
  • Example 6 The specific preparation procedure of this example is the same as that of Example 6, but the stoichiometry of the precursor compounds Na 2 CO 3 (analytical grade), Fe 2 O 3 , CuO, Mn 2 O 3 used is different from that in Example 6, and a black powder is obtained.
  • the layered oxide material is Na 0.875 Cu 0.2 Fe 0.4 Mn 0.4 O 2 , and its XRD pattern is similar to that of FIG.
  • the layered 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 6.
  • the test voltage range is from 2.5V to 4.0V, and the test results are shown in Figure 13.
  • the first and second week charge and discharge curves are shown in FIG. It can be seen that the first week discharge specific capacity can reach 91.4 mAh / g, the first week Coulomb efficiency is about 93.3%.
  • the layered oxide material is prepared by the solid phase method described in the foregoing embodiment 2.
  • Example 6 The specific preparation procedure of this example is the same as that of Example 6, except that the precursor compounds Na 2 CO 3 (analytical grade), NiO, Fe 2 O 3 , CuO, Mn 2 O 3 and MnO 2 are stoichiometrically and in Example 6. Differently, the layered oxide material obtained as a black powder was Na 0.9 Cu 0.2 Fe 0.3 Mn 0.43 Ni 0.07 O 2 , and its XRD pattern is shown in Fig. 1 .
  • the layered 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 6.
  • the test voltage range is from 2.5V to 4.1V, and the test results are shown in Figure 14.
  • 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 112.6 mAh / g, the first week Coulomb efficiency is about 86.4%.
  • the layered oxide material is prepared by the solid phase method described in the foregoing embodiment 2.
  • Example 6 The specific preparation procedure of this example is the same as that of Example 6, but the stoichiometry and implementation of the precursor compounds Na 2 CO 3 (analytical grade), Al 2 O 3 , Fe 2 O 3 , CuO, Mn 2 O 3 and MnO 2 are used .
  • the layered oxide material obtained as a black powder was Na 0.9 Cu 0.225 Fe 0.3 Mn 0.425 Al 0.05 O 2 , and its XRD pattern is shown in Fig. 1.
  • Figure 15 is a scanning electron micrograph of Na 0.9 Cu 0.225 Fe 0.3 Mn 0.425 Al 0.05 O 2 . It can be seen from the figure that the particle size distribution of Na 0.9 Cu 0.225 Fe 0.3 Mn 0.425 Al 0.05 O 2 is mainly from 1 ⁇ m to 10 Micron.
  • the layered 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 6.
  • the test voltage range is 2.5V to 4.0V, and the test results are shown in Figure 16.
  • the first and second week charge and discharge curves are shown in FIG. It can be seen that the first week discharge specific capacity can reach 106.1 Ah/g, and the first week coulombic efficiency is 91.7%.
  • the layered oxide material is prepared by the solid phase method described in the foregoing embodiment 2.
  • Example 6 The specific preparation procedure of this example is the same as that of Example 6, but the stoichiometry of the precursor compounds Na 2 CO 3 (analytical grade), Fe 2 O 3 , CuO, Mn 2 O 3 used is different from that in Example 6, and a black powder is obtained.
  • the layered oxide material was Na 0.95 Cu 0.225 Fe 0.35 Mn 0.425 O 2 , and its XRD pattern was similar to that of FIG.
  • the layered 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 6.
  • the test voltage range is 2.5V to 4.0V, and the test results are shown in Figure 17.
  • the first and second week charge and discharge curves are shown in FIG. It can be seen that the first week discharge specific capacity can reach 104 mAh / g, the first week Coulomb efficiency is about 93.1%.
  • the layered oxide material is prepared by the solid phase method described in the foregoing embodiment 2.
  • Example 6 The specific preparation steps of this example are the same as those of Example 6, but the stoichiometry of the precursor compounds Na 2 CO 3 (analytical grade), Fe 2 O 3 , CuO, Mn 2 O 3 and MnO 2 used is different from that in Example 6.
  • the layered oxide material obtained as a black powder was NaCu 0.225 Fe 0.3 Mn 0.475 O 2 , and its XRD pattern was similar to that of FIG.
  • the layered 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 6.
  • the test voltage range is 2.5V to 4.0V, and the test results are shown in Figure 18. Shown in Figure 18 The first and second weeks of charge and discharge curves. It can be seen that the first week discharge specific capacity can reach 89.1 mAh / g, the first week Coulomb efficiency is about 89.2%.
  • the layered oxide material is prepared by the solid phase method described in the foregoing embodiment 2.
  • Example 6 The specific preparation procedure of this example is the same as that of Example 6, but the stoichiometry of the precursor compounds Na 2 CO 3 (analytical grade), Fe 2 O 3 , CuO, Mn 2 O 3 used is different from that in Example 6, and a black powder is obtained.
  • the layered oxide material is Na 0.875 Cu 0.22 Fe 0.25 Mn 0.53 O 2 , and its XRD pattern is similar to that of FIG.
  • the layered 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 6.
  • the test voltage range is 2.5V to 4.1V, and the test results are shown in Figure 19.
  • the first and second weeks of charge and discharge curves are shown in FIG. It can be seen that the first week discharge specific capacity can reach 87.4 mAh / g, the first week Coulomb efficiency is about 80.0%.
  • the layered oxide material is prepared by the solid phase method described in the foregoing embodiment 2.
  • Example 6 The specific preparation steps of this example are the same as those of Example 6, but the stoichiometry of the precursor compounds Na 2 CO 3 (analytical grade), Fe 2 O 3 , CuO, Mn 2 O 3 and MnO 2 used is different from that in Example 6.
  • the layered oxide material obtained as a black powder was Na 0.833 Cu 0.2 Fe 0.4 Mn 0.4 O 2 , and its XRD pattern was similar to that of FIG.
  • the layered 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 6.
  • the test voltage range is from 2.5V to 4.1V, and the test results are shown in Figure 20.
  • the first and second weeks of charge and discharge curves are shown in FIG. It can be seen that the first week discharge specific capacity can reach 105.9 mAh / g, the first week Coulomb efficiency is about 90.2%.
  • the layered oxide material was prepared by the spray drying method described in the foregoing Example 3.
  • a stoichiometric ratio of sodium nitrate, copper nitrate, iron nitrate, and manganese acetate precursor is weighed, and the precursor is dissolved in water to obtain a transparent solution; the solution is placed in a spray dryer and spray dried at 130 ° C.
  • the collected precursor was transferred to an alumina crucible and heat-treated at 750 ° C for 6 hours in a muffle furnace to obtain a dark brown powder layered oxide material of Na 0.9 Cu 0.225 Fe 0.3 Mn 0.475 O 2 .
  • the XRD pattern is similar to that of Figure 1.
  • Figure 21 is an SEM image of Na 0.9 Cu 0.225 Fe 0.3 Mn 0.475 O 2 . As can be seen from the figure, the material has an average particle size of 1 ⁇ m.
  • the layered 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 6.
  • the test voltage range is from 2.5V to 4.1V, and the test results are shown in Figure 22.
  • the first and second week charge and discharge curves are shown in FIG. It can be seen that the first week discharge specific capacity can reach 101 mAh / g, the first week Coulomb efficiency is about 76%.
  • the layered oxide material was prepared by the sol-gel method described in the above Example 4.
  • the specific preparation steps of the present embodiment are: firstly, the precursor compounds NaNO 3 , Fe(NO 3 ) 3 , Cu(NO 3 ) 2 , and Mn(C 2 H 3 O 2 ) 2 are sequentially dissolved in a stoichiometric ratio.
  • the layered 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 6.
  • the test voltage range is from 2.5V to 4.1V, and the test results are shown in Figure 24.
  • the first and second weeks of charge and discharge curves are shown in FIG. It can be seen that the first week discharge specific capacity can reach 98.6 mAh / g, the first week Coulomb efficiency is about 79.6%, and has good cycle stability.
  • the layered oxide material was prepared by the sol-gel method described in the above Example 4.
  • Example 20 The specific preparation steps in this example are as in Example 20, but the stoichiometric ratios of the precursor compounds NaNO 3 , Fe(NO 3 ) 3 , Cu(NO 3 ) 2 , Mn(C 2 H 3 O 2 ) 2 and the examples are used.
  • the obtained dry gel was transferred to an alumina crucible, and calcined at 200 ° C for 2 hours; and then heat treated at 700 ° C for 10 hours in an air atmosphere in a muffle furnace to obtain a reddish brown black powder.
  • the layered oxide material was Na 0.9 Cu 0.27 Fe 0.3 Mn 0.43 O 2 , and its XRD pattern was similar to that of FIG.
  • the layered 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 6.
  • the test voltage range is from 2.5V to 4.1V, and the test results are shown in Figure 25.
  • the first and second week charge and discharge curves are shown in FIG. It can be seen that the first week discharge specific capacity can reach 98.3 mAh / g, the first week Coulomb efficiency is about 87.8%.
  • the layered oxide material was prepared by the coprecipitation method described in the foregoing Example 5. Specifically include:
  • the precursors such as copper nitrate, ferric nitrate and manganese acetate are dissolved in deionized water according to the stoichiometric ratio; the previously prepared aqueous solution of copper nitrate, ferric nitrate and manganese acetate is slowly added to a certain concentration by a peristaltic pump tube. After the reaction is completed, the formed precipitate is taken out and washed with deionized water, and dried in a vacuum oven at 80 ° C; the dried powder and sodium carbonate are uniformly mixed in a stoichiometric ratio to obtain a precursor; The precursor was transferred to a muffle furnace and heat treated at 800 ° C for 12 hours.
  • the powder after the heat treatment was ground to obtain a black layered oxide material of Na 0.95 Cu 0.225 Fe 0.25 Mn 0.525 O 2 . Its XRD is similar to that shown in Figure 1.
  • the layered 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 6.
  • the test voltage range is from 2.5V to 4.1V.
  • the first week discharge specific capacity is up to 99mAh/g, and the first week Coulomb efficiency is about 89%.
  • the layered 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 6, but the stoichiometry of the precursor compounds Na 2 CO 3 (analytical grade), Fe 2 O 3 , CuO, Mn 2 O 3 and MgO used is different from that in Example 6, and The final heat treatment temperature was 950 ° C for 10 hours, and the layered oxide material obtained as a black powder was Na 0.9 Cu 0.2 Fe 0.3 Mn 0.45 Mg 0.05 O 2 , and its XRD pattern was similar to FIG.
  • the layered 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 6.
  • the test voltage range is from 2.5V to 4.1V.
  • the first week discharge specific capacity is up to 96mAh/g, and the first week Coulomb efficiency is about 90.1%.
  • the layered 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 6, except that the precursor compounds Na 2 CO 3 (analytical grade), Fe 2 O 3 , CuO, Mn 2 O 3 and B 2 O 3 are stoichiometrically and in Example 6.
  • the final heat treatment temperature was 900 ° C, 12 hours
  • the layered oxide material obtained as a black powder was Na 0.9 Cu 0.225 Fe 0.3 Mn 0.425 B 0.05 O 2
  • its XRD pattern was similar to FIG.
  • the layered 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 6.
  • the test voltage range is 2.5V ⁇ 4.1V
  • the first week discharge specific capacity can reach 98mAh / g
  • the first week Coulomb efficiency is about 89%.
  • the layered 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 6, except that the precursor compounds Na 2 CO 3 (analytical grade), Fe 2 O 3 , CuO, Mn 2 O 3 and Co 2 O 3 are stoichiometrically and in Example 6.
  • the final heat treatment temperature was 800 ° C for 12 hours
  • the layered oxide material obtained as a black powder was Na 0.9 Cu 0.225 Fe 0.3 Mn 0.455 Co 0.02 O 2
  • its XRD pattern was similar to FIG.
  • the layered 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 6.
  • the test voltage range is 2.5V ⁇ 4.1V
  • the first week discharge specific capacity can reach 107mAh / g
  • the first week Coulomb efficiency is about 91.5%.
  • the layered oxide material is prepared by the solid phase method described in the foregoing embodiment 2.
  • Example 6 The specific preparation steps of this example are the same as those of Example 6, but the stoichiometry of the precursor compounds Na 2 CO 3 (analytical grade), Fe 2 O 3 , CuO, Mn 2 O 3 and NiO used is different from that in Example 6, and The final heat treatment temperature was 800 ° C for 12 hours, and the layered oxide material obtained as a black powder was Na 0.9 Cu 0.2 25 Fe 0.3 Mn 0.425 Ni 0.05 O 2 , and its XRD pattern was similar to that of FIG.
  • the layered 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 6.
  • the test voltage range is 2.5V to 4.05V, and the test results are shown in Figure 26.
  • the first and second week charge and discharge curves are shown in FIG. It can be seen that the first week discharge specific capacity can reach 104.7 mAh / g, the first week Coulomb efficiency is about 90.1%.
  • the material and the hard carbon are assembled into a full battery, and the test voltage ranges from 1.5V to 4.05V.
  • the test result is shown in FIG. 27, and the first week and second week curves of charging and discharging with C/5 current are shown in FIG. 27; It can be seen that the first week discharge specific capacity is 307.9 mAh / g (calculated as the mass of the negative active material), and the first week Coulomb efficiency is about 76%.
  • the layered oxide material provided by the embodiment of the invention is simple to prepare, and the transition metal copper, iron and manganese contained therein are all non-toxic and safe elements, and the abundance in the earth's crust is high, so the manufacturing cost is low.
  • a sodium ion secondary battery using the layered oxide material of the present invention depending on the price of divalent to trivalent copper, the price of trivalent to tetravalent iron, and the price of trivalent to tetravalent manganese, achieves a relatively high first week
  • the charging capacity, excellent cycle performance, good safety performance, and great practical value can be used for large-scale energy storage equipment of solar power generation, wind power generation, smart grid peak shaving, distributed power station, backup power source or communication base station.

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Abstract

本发明公开了一种层状氧化物材料、制备方法、极片、二次电池和用途，所述材料的化学通式为：NaxCuiFejMnkMyO2+β；M为对过渡金属位进行掺杂取代的元素；所述x，y，i，j，k，β分别为对应元素所占的摩尔百分比；其中x，y，i，j，k，β之间的关系满足y+i+j+k＝1，且x+my+2i+3j+4k＝2(2+β)；其中0.8≤x≤1；0<i≤0.3；0<j≤0.5；0<k≤0.5；-0.02≤β≤0.02；m为所述M的化合价态；所述层状氧化物材料的空间群为R3̄m。

Description

一种层状氧化物材料、制备方法、极片、二次电池和用途 技术领域
本发明涉及材料技术领域，尤其涉及一种层状氧化物材料、制备方法、极片、二次电池和用途。
背景技术
随着石油、煤等不可再生能源的减少和环境污染的加剧，发展清洁能源成为全球性的课题。发展风能、太阳能和与之配套的储能电池等成为解决这一课题的关键。现有的电化学储能设备主要有铅酸电池、锌-镍电池、氢-镍电池、液流电池及锂离子电池等。其中锂离子二次电池多数采用锂离子嵌入化合物作为正负极材料，以干燥的有机溶剂作为电解液；锂离子可逆的在正负极活性物质之间来回脱嵌，并且不会破坏材料的结构。锂离子电池由于工作电压高(3.6V)，是镉-镍、氢-镍电池的三倍；体积小，比氢-镍电池小30％；质量轻，比氢-镍电池轻50％；比能量高(200Wh/kg)，是镉-镍电池的2-3倍；无记忆效应、无污染、自放电小、循环寿命长，成为公认最有希望成为电动汽车的动力电池以及可再生能源的储能电池。但是，因为锂资源有限且提取成本高，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的元素钠与锂具有非常相似的物理和化学性质，并且钠在地球上的丰度比锂要高，成本较低，所以发展钠离子二次电池作为大规模储能设备成为一个比较好的选择。
近年来由于锂资源的有限，钠资源的丰富，钠离子二次电池已经被广泛研究。目前已有大量的文献报道作为钠离子电池的电极材料；其中正极材料主要包括NASCION结构的Na3V2(PO4)3【Electrochem.Commun.,2012, 14,86-89，Adv.Energy Mater.,2013,3,156-160】,NaVPO4,Na3V2(PO4)3F3【J.Mater.Chem.,2012,22,20535-20541】,Na3V2O(PO4)3F，NaTi2(PO4)3等，但是由于这类材料电子电导率很低，动力学性能比较差，常常需要通过纳米化和碳包覆才能得到比较稳定的循环，并且其中所含的钒元素也是有毒元素，所以应用起来比较难。最早等人提出的隧道型结构的Na4Mn9O18【Adv.Mater.,2011,23,3155-3160】的结构，其中可以移动的钠离子处在S型的大通道内，这个结构在整个循环过程中非常稳定，可以做到2000次的长循环，但是由于这个结构主要依靠锰三价到锰四价的变化，并且原始钠含量比较低，所以整个正极材料平均电压较低，且容量比较低。
层状正极材料也是近年来大家研究的热点，P2相的NaxTMO2和O3相的NaTMO2是目前研究最多的材料【Phys ica l B&C,1980,99,81-85】，O3相的钠含量高，首周充电容量高，但是其电化学循环性能差，而且对于空气和水敏感，应用起来有一定难度；P2相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，钠离子的脱嵌比较快，但是大部分P2相材料在空气中不稳定且由于钠含量比较低其首周充电容量一般较低。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2.0-4.5V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。
此外，目前现有的层状氧化物要达到首周充电容量高、效率高、倍率性能好、循环性好，都必须要含有镍或者钴作为变价元素。而这两种元素的化合物成本高并且有毒、不环保。
发明内容
本发明实施例提供了一种层状氧化物材料、制备方法、极片、二次电池和用途。所述层状氧化物材料制备简单，所含有的过渡金属铜、铁、锰都是 无毒安全的元素，在地壳中的丰度高，因此制造成本低廉。应用本发明的层状氧化物材料的钠离子二次电池，首周效率高，循环性能优异，安全性能好，具有很大实用价值，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氧化物材料，化学通式为：NaxCuiFejMnkMyO2+β；
其中，M为对过渡金属位进行掺杂取代的元素，具体为Li+，Ni2+,Mg2+,Mn2+,Zn2+,Co2+,Ca2+,Ba2+,Sr2+,Mn3+,Al3+,B3+,Cr3+,Co3+,V3+,Zr4+，Ti4+,Sn4+,V4+,Mo4+,Mo5+，Ru4+，Nb5+,Si4+,Sb5+,Nb5+,Mo6+，Te6+中的一种或多种；
所述x，y，i，j,k,β分别为对应元素所占的摩尔百分比；其中x，y，i，j,k,β之间的关系满足y+i+j+k＝1，且x+my+2i+3j+4k＝2(2+β)；其中0.8≤x≤1；0<i≤0.3；0<j≤0.5；0<k≤0.5；-0.02≤β≤0.02；m为所述M的化合价态；
所述层状氧化物材料的空间群为R3m。
优选的，所述层状氧化物材料用于钠离子二次电池的正极活性材料。
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100wt％～108wt％的碳酸钠和所需化学计量的氧化铜、氧化铁、氧化锰和M的氧化物按比例混合成前驱体；所述M具体为Li+，Ni2+,Mg2+,Mn2+,Zn2+,Co2+,Ca2+,Ba2+,Sr2+,Mn3+,Al3+,B3+,Cr3+,Co3+,V3+,Zr4+，Ti4+,Sn4+,V4+,Mo4+,Mo5+，Ru4+，Nb5+,Si4+,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700℃～1000℃的空气气氛中热处理2～24小时；
将热处理后的前驱体粉末进行研磨，得到所述层状氧化物材料。
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100wt％～108wt％的碳酸钠和所需化学计量的氧化铜、氧化铁、氧化锰和M的氧化物按比例混合成前驱体；所述M具体为Li+，Ni2+,Mg2+,Mn2+,Zn2+,Co2+,Ca2+,Ba2+,Sr2+,Mn3+,Al3+,B3+,Cr3+,Co3+,V3+,Zr4+，Ti4+,Sn4+,V4+,Mo4+,Mo5+，Ru4+，Nb5+,Si4+,Sb5+,Nb5+,Mo6+，Te6+中的一种或多种；将所述前驱体加乙醇或水后搅拌均匀形成浆料；
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650℃～1000℃的空气气氛中热处理2～24小时；
将热处理后的前驱体粉末进行研磨，得到所述层状氧化物材料。
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氧化物材料的制备方法，所述方法为喷雾干燥法，包括：
采用化学计量比的硝酸钠、硝酸铜、硝酸铁、乙酸锰和M的硝酸盐为前驱体；所述M具体为Li+，Ni2+,Mg2+,Mn2+,Zn2+,Co2+,Ca2+,Ba2+,Sr2+,Mn3+,Al3+,B3+,Cr3+,Co3+,V3+,Zr4+，Ti4+,Sn4+,V4+,Mo4+,Mo5+，Ru4+，Nb5+,Si4+,Sb5+,Nb5+,Mo6+，Te6+中的一种或多种；
将所述前驱体加乙醇或水后搅拌均匀形成浆料；
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650℃ˉ1000℃的空气气氛中热处理2～24小时；
将热处理后的前驱体粉末进行研磨，得到所述层状氧化物材料。
第五方面，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100wt％～108wt％的乙酸钠或硝酸钠或碳酸钠或硫酸钠、含有铜、铁、锰、掺杂元素M的硝酸盐或硫酸盐按化学计量比溶于水或者溶于乙醇混合成前驱体溶液；所述M具体为Li+， Ni2+,Mg2+,Mn2+,Zn2+,Co2+,Ca2+,Ba2+,Sr2+,Mn3+,Al3+,B3+,Cr3+,Co3+,V3+,Zr4+，Ti4+,Sn4+,V4+,Mo4+,Ru4+，Mo5+，Nb5+,Si4+,Sb5+,Nb5+,Mo6+，Te6+中的一种或多种；
在50℃～100℃下搅拌，并且加入适量螯合剂，蒸干形成前驱体凝胶；
将所述前驱体凝胶置于坩埚中，在200～500℃的空气气氛下，预烧2个小时；
再在600℃～1000℃下热处理2～24小时；
将热处理后的前驱体粉末进行研磨，得到所述层状氧化物材料。
第六方面，本发明实施例提供了一种如上述第一方面所述的层状氧化物材料的制备方法，所述方法为共沉淀法，包括：
将所需化学计量比的含有铜、铁、锰和M的硝酸盐或硫酸盐或碳酸盐或者氢氧化物分别溶于一定体积的去离子水中，并分别形成溶液；
用蠕动泵将所述溶液缓慢的滴加在一定浓度和pH值的氨水溶液中，生成沉淀物；
将得到的沉淀物用去离子水清洗干净，烘干后与碳酸钠按照化学计量比均匀混合得到的前驱物；
将所述前驱物置于坩埚中，在600℃～1000℃的空气气氛下，热处理6～24个小时，得到前驱体粉末；
将热处理后的前驱体粉末进行研磨，得到所述层状氧化物材料。
第七方面，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氧化物材料。
第八方面，本发明实施例提供了一种包括上述第七方面所述的正极极片的钠离子二次电池。
第九方面，本发明实施例提供了一种如上述第八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氧化物材料制备简单，所含有的过渡金属铜、铁、锰都是无毒安全的元素，在地壳中的丰度高，因此制造成本低廉。应用本发明的层状氧化物材料的钠离子二次电池，依靠二价到三价铜转变，三价到四价铁的转变和三价到四价锰的变价实现比较高的首周充电容量，循环性能优异，安全性能好，具有很大实用价值，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氧化物材料的XRD图谱；
图2为本发明实施例2提供的固相法制备层状氧化物材料的制备方法流程图；
图3为本发明实施例3提供的喷雾干燥法制备层状氧化物材料的制备方法流程图；
图4为本发明实施例4提供的溶胶-凝胶法制备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提供的共沉淀法制备层状含铜氧化物材料的制备方法流程图；
图6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7为本发明实施例7提供的NaCu0.15Fe0.4Mn0.35Ni0.1O2的SEM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提供的一种钠离子电池的充放电曲线图；
图15为本发明实施例14提供的Na0.9Cu0.225Fe0.3Mn0.425Al0.05O2的SEM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；
图17为本发明实施例15提供的一种钠离子电池的充放电曲线图；
图18为本发明实施例16提供的一种钠离子电池的充放电曲线图；
图19为本发明实施例17提供的一种钠离子电池的充放电曲线图；
图20为本发明实施例18提供的一种钠离子电池的充放电曲线图；
图21为本发明实施例19提供的Na0.9Cu0.225Fe0.3Mn0.475O2的SEM图；
图22为本发明实施例19提供的一种钠离子电池的充放电曲线图；
图23为本发明实施例20提供的Na0.9Cu0.225Fe0.3Mn0.475O2的SEM图；
图24为本发明实施例20提供的一种钠离子电池的充放电曲线图；
图25为本发明实施例21提供的一种钠离子电池的充放电曲线图；
图26为本发明实施例26提供的一种钠离子电池的充放电曲线图；
图27为本发明实施例26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提供了一种层状氧化物材料，其的化学通式为：NaxCuiFejMnkMyO2+β；
其中，M为对过渡金属位进行掺杂取代的元素，具体为Li+，Ni2+,Mg2+,Mn2+,Zn2+,Co2+,Ca2+,Ba2+,Sr2+,Mn3+,Al3+,B3+,Cr3+,Co3+,V3+,Zr4+，Ti4+, Sn4+,V4+,Mo4+,Mo5+，Ru4+，Nb5+,Si4+,Sb5+,Nb5+,Mo6+，Te6+中的一种或多种；
所述x，y，i，j,k,β分别为对应元素所占的摩尔百分比；其中x，y，i，j,k,β之间的关系满足y+i+j+k＝1，且x+my+2i+3j+4k＝2(2+β)；其中0.8≤x≤1；0<i≤0.3；0<j≤0.5；0<k≤0.5；-0.02≤β≤0.02；m为所述M的化合价态；
所述层状氧化物材料的空间群为R3m。
在图1中给出了不同元素摩尔百分比的多个层状氧化物材料的X射线衍射(X-ray diffract ion,XRD)图谱，由XRD图谱可以看出，本实施例提供的NaxCuiFejMnkMyO2+β的晶体结构为O3相的层状结构的氧化物。
本实施例提供的层状氧化物材料，制备简单，所含有的过渡金属铜、铁、锰都是无毒安全的材料，在地壳中的丰富度高，因此制造成本低廉。可以应用于钠离子二次电池的正极活性材料。应用本发明的层状氧化物材料的钠离子二次电池，依靠二价到三价铜转变，三价到四价铁的转变和三价到四价锰的变价实现比较高的首周充电容量，循环性能优异，安全性能好，具有很大实用价值。
实施例2
本实施例提供了一种层状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100wt％～108wt％的碳酸钠和所需化学计量的氧化铜、氧化铁、氧化锰和M的氧化物按比例混合成前驱体；
具体的，所述M具体为Li+，Ni2+,Mg2+,Mn2+,Zn2+,Co2+,Ca2+,Ba2+,Sr2+,Mn3+,Al3+,B3+,Cr3+,Co3+,V3+,Zr4+，Ti4+,Sn4+,V4+,Mo4+,Mo5+，Ru4+，Nb5+,Si4+,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700℃～1000℃的空气 气氛中热处理2～24小时；
步骤204，将热处理后的前驱体粉末进行研磨，得到所述层状氧化物材料。
本实施例提供的层状氧化物材料的制备方法，能够用于制备上述实施例1中所述的层状氧化物材料。本实施例提供的方法简单易行、成本低廉、所用材料安全无毒，适用于大规模制造的应用。
实施例3
本实施例提供了一种层状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100wt％～108wt％的碳酸钠和氧化铜、氧化铁、氧化锰和M的氧化物按比例称量混合成前驱体；或者采用化学计量比的硝酸钠，硝酸铜，硝酸铁，乙酸锰和M的硝酸盐为前驱体；
具体的，所述M可以为Li+，Ni2+,Mg2+,Mn2+,Zn2+,Co2+,Ca2+,Ba2+,Sr2+,Mn3+,Al3+,B3+,Cr3+,Co3+,V3+,Zr4+，Ti4+,Sn4+,V4+,Mo4+,Mo5+，Ru4+，Nb5+,Si4+,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650℃～1000℃的空气气氛中热处理2～24小时；
步骤305，将热处理后的前驱体粉末进行研磨，得到所述层状氧化物材料。
本实施例提供的层状氧化物材料的制备方法，能够用于制备上述实施例1中所述的层状氧化物材料。本实施例提供的方法简单易行、成本低廉、所用材料安全无毒，适用于大规模制造的应用。
实施例4
本实施例提供了一种层状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100wt％～108wt％的乙酸钠或硝酸钠或碳酸钠或硫酸钠、含有铜、铁、锰、掺杂元素M的硝酸盐或硫酸盐按化学计量比溶于水或者溶于乙醇混合成前驱体溶液；
其中，所述M具体为Li+，Ni2+,Mg2+,Mn2+,Zn2+,Co2+,Ca2+,Ba2+,Sr2+,Mn3+,Al3+,B3+,Cr3+,Co3+,V3+,Zr4+，Ti4+,Sn4+,V4+,Mo4+,Ru4+，Mo5+，Nb5+,Si4+,Sb5+,Nb5+,Mo6+，Te6+中的一种或多种。
步骤402，在50℃～100℃下搅拌，并且加入适量螯合剂，蒸干形成前驱体凝胶；
步骤403，将所述前驱体凝胶置于坩埚中，在200℃～500℃的空气气氛下，预烧2个小时；
步骤404，再在600℃～1000℃下热处理2～24小时；
步骤405，将热处理后的前驱体粉末进行研磨，得到所述层状氧化物材料。
本实施例提供的层状氧化物材料的制备方法，能够用于制备上述实施例1中所述的层状氧化物材料。本实施例提供的方法简单易行、成本低廉、所用材料安全无毒，适用于大规模制造的应用。
实施例5
本实施例提供了一种层状氧化物材料的制备方法，具体为共沉淀法，如图5所示，包括：
步骤501，将所需化学计量比的含有铜、铁、锰和M的硝酸盐或硫酸盐或碳酸盐或者氢氧化物分别溶于一定体积的去离子水中，并分别形成溶液；
其中，所述M具体为Li+，Ni2+,Mg2+,Mn2+,Zn2+,Co2+,Ca2+,Ba2+,Sr2+,Mn3+,Al3+,B3+,Cr3+,Co3+,V3+,Zr4+，Ti4+,Sn4+,V4+,Mo4+,Ru4+，Mo5+，Nb5+,Si4+,Sb5+,Nb5+,Mo6+，Te6+中的一种或多种。
步骤502，用蠕动泵将所述溶液缓慢的滴加在一定浓度和pH值的氨水溶液中，生成沉淀物；
步骤503，将得到的沉淀物用去离子水清洗干净，烘干后与碳酸钠按照化学计量比均匀混合得到的前驱物；
步骤504，将所述前驱物置于坩埚中，在600℃～1000℃的空气气氛下，热处理2～24个小时，得到前驱体粉末；
步骤505，将热处理后的前驱体粉末进行研磨，得到所述层状氧化物材料。
本实施例提供的层状氧化物材料的制备方法，能够用于制备上述实施例1中所述的层状氧化物材料。本实施例提供的方法简单易行、成本低廉、所用材料安全无毒，适用于大规模制造的应用。
为更好的理解本发明提供的技术方案，下述以多个具体实例分别说明应用本发明上述实施例提供的几种方法制备层状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6
本实施例中采用前述实施例2所述的固相法制备层状氧化物材料，包括：
将Na2CO3(分析纯)、Fe2O3(分析纯)、CuO、Mn2O3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；将前驱体压片后转移到Al2O3坩埚内，在马弗炉中850℃下处理12小时，得到黑色粉末的层状氧化物材料NaCu0.2Fe0.4Mn0.4O2，其XRD图谱参见图1，从XRD图谱上看，NaCu0.2Fe0.4Mn0.4O2 的晶体结构为O3相层状结构的氧化物。
将上述制备得到的层状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NaCu0.2Fe0.4Mn0.4O2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，110℃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4.1V的条件下，测试结果见图6。图6中示出了第一周和第二周的充放电循环曲线，可以看出，其首周放电比容量可达90.4mAh/g，首周库仑效率约为82.3％，循环非常稳定。
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氧化物材料。
实施例的具体制备步骤同实施例6，但所用前驱体化合物Na2CO3(分析纯)、NiO(分析纯)、Fe2O3、CuO、Mn2O3、MnO2的化学计量与实施例6中不同，热处理条件为950℃、10小时，得到黑色粉末的层状氧化物材料为NaCu0.15Fe0.4Mn0.35Ni0.1O2，其XRD图谱参见图1。图7为NaCu0.15Fe0.4Mn0.35Ni0.1O2的扫描电子显微镜(SEM)图，从图中可以看出，该材料的颗粒尺寸分布主要从1微米到10微米。
将上述制备得到的层状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6。测试电压范围为2.5V～4.0V，测试结果见图8。图8中示出了 第一周及第二周充放电曲线。可以看出，首周放电比容量可达105.3mAh/g，首周库仑效率约为93.8％。
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氧化物材料。
本实施例的具体制备步骤同实施例6，但所用前驱体化合物Na2CO3(分析纯)、Fe2O3、CuO、MnO2及TiO2的化学计量与实施例6中不同，得到黑色粉末的层状氧化物材料为NaCu0.1Fe0.5Mn0.3Ti0.1O2，其XRD图谱参见图1。
将上述制备得到的层状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6。测试电压范围为2.5V～4.0V，测试结果见图9。图9中示出了第一周及第二周充放电曲线。可以看出，首周放电比容量可达97.6mAh/g，首周库仑效率约为89.7％。
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氧化物材料。
本实本实施例的具体制备步骤同实施例6，但所用前驱体化合物Na2CO3(分析纯)、Fe2O3、CuO、Mn2O3及TiO2的化学计量与实施例6中不同，得到黑色粉末的层状氧化物材料为NaCu0.2Fe0.4Mn0.3Ti0.1O2，其XRD图谱与图1类似。
将上述制备得到的层状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6。测试电压范围为2.5V～4.0V，测试结果见图10。图10中示出了第一周及第二周充放电曲线。可以看出，首周放电比容量可达90.1mAh/g，首周库仑效率约为88％。
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氧化物材料。
本实施例的具体制备步骤同实施例6，但所用前驱体化合物Na2CO3(分析纯)、Fe2O3、CuO、Mn2O3及MnO2的化学计量与实施例6中不同，得到黑色粉末的层状氧化物材料为Na0.9Cu0.225Fe0.3Mn0.475O2，其XRD图谱与图1类似。
将上述制备得到的层状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6。测试电压范围为2.5V～4.1V，测试结果见图11。图11中示出了第一周及第二周充放电曲线。可以看出，首周放电比容量可达101.4mAh/g，首周库仑效率约为89.8％。
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氧化物材料。
本实施例的具体制备步骤同实施例6，但所用前驱体化合物Na2CO3(分析纯)、Fe2O3、CuO及Mn2O3的化学计量与实施例6中不同，得到黑色粉末的层状氧化物材料为Na0.833Cu0.167Fe0.333Mn0.5O2，其XRD图谱参见图1。
将上述制备得到的层状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6。测试电压范围为2.5V～4.1V，测试结果见图12。图12中示出了第一周及第二周充放电曲线。可以看出，首周放电比容量可达86.2mAh/g，首周库仑效率约为85.7％。
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氧化物材料。
本实施例的具体制备步骤同实施例6，但所用前驱体化合物Na2CO3(分析纯)、Fe2O3、CuO、Mn2O3的化学计量与实施例6中不同，得到黑色粉末 的层状氧化物材料为Na0.875Cu0.2Fe0.4Mn0.4O2，其XRD图谱与图1类似。
将上述制备得到的层状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6。测试电压范围为2.5V～4.0V，测试结果见图13。图13中示出了第一周及第二周充放电曲线。可以看出，首周放电比容量可达91.4mAh/g，首周库仑效率约为93.3％。
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氧化物材料。
本实施例的具体制备步骤同实施例6，但所用前驱体化合物Na2CO3(分析纯)、NiO、Fe2O3、CuO、Mn2O3及MnO2的化学计量与实施例6中不同，得到黑色粉末的层状氧化物材料为Na0.9Cu0.2Fe0.3Mn0.43Ni0.07O2，其XRD图谱参见图1。
将上述制备得到的层状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6。测试电压范围为2.5V～4.1V，测试结果见图14。图14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112.6mAh/g，首周库仑效率约为86.4％。
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氧化物材料。
本实施例的具体制备步骤同实施例6，但所用前驱体化合物Na2CO3(分析纯)、Al2O3、Fe2O3、CuO、Mn2O3及MnO2的化学计量与实施例6中不同，得到黑色粉末的层状氧化物材料为Na0.9Cu0.225Fe0.3Mn0.425Al0.05O2，其XRD图谱参见图1。图15为Na0.9Cu0.225Fe0.3Mn0.425Al0.05O2的扫描电子显微镜图，从图中可以看出，Na0.9Cu0.225Fe0.3Mn0.425Al0.05O2的颗粒尺寸分布主要从1微米到10 微米。
将上述制备得到的层状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6。测试电压范围为2.5V～4.0V，测试结果见图16。图16中示出了第一周及第二周充放电曲线。可以看出，首周放电比容量可达106.1Ah/g，首周库仑效率为91.7％。
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氧化物材料。
本实施例的具体制备步骤同实施例6，但所用前驱体化合物Na2CO3(分析纯)、Fe2O3、CuO、Mn2O3的化学计量与实施例6中不同，得到黑色粉末的层状氧化物材料为Na0.95Cu0.225Fe0.35Mn0.425O2，其XRD图谱与图1类似。
将上述制备得到的层状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6。测试电压范围为2.5V～4.0V，测试结果见图17。图17中示出了第一周及第二周充放电曲线。可以看出，首周放电比容量可达104mAh/g，首周库仑效率约为93.1％。
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氧化物材料。
本实施例的具体制备步骤同实施例6，但所用前驱体化合物Na2CO3(分析纯)、Fe2O3、CuO、Mn2O3及MnO2的化学计量与实施例6中不同，得到黑色粉末的层状氧化物材料为NaCu0.225Fe0.3Mn0.475O2，其XRD图谱与图1类似。
将上述制备得到的层状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6。测试电压范围为2.5V～4.0V，测试结果见图18。图18中示出 了第一周及第二周充放电曲线。可以看出，首周放电比容量可达89.1mAh/g，首周库仑效率约为89.2％。
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氧化物材料。
本实施例的具体制备步骤同实施例6，但所用前驱体化合物Na2CO3(分析纯)、Fe2O3、CuO、Mn2O3的化学计量与实施例6中不同，得到黑色粉末的层状氧化物材料为Na0.875Cu0.22Fe0.25Mn0.53O2，其XRD图谱与图1类似。
将上述制备得到的层状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6。测试电压范围为2.5V～4.1V，测试结果见图19。图19中示出了第一周及第二周充放电曲线。可以看出，首周放电比容量可达87.4mAh/g，首周库仑效率约为80.0％。
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氧化物材料。
本实施例的具体制备步骤同实施例6，但所用前驱体化合物Na2CO3(分析纯)、Fe2O3、CuO、Mn2O3及MnO2的化学计量与实施例6中不同，得到黑色粉末的层状氧化物材料为Na0.833Cu0.2Fe0.4Mn0.4O2，其XRD图谱与图1类似。
将上述制备得到的层状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6。测试电压范围为2.5V～4.1V，测试结果见图20。图20中示出了第一周及第二周充放电曲线。可以看出，首周放电比容量可达105.9mAh/g，首周库仑效率约为90.2％。
实施例19
本实施例中采用前述实施例3所述的喷雾干燥法制备层状氧化物材料。
本实施例中称取化学计量比的硝酸钠，硝酸铜，硝酸铁，乙酸锰前驱物，将前驱物溶解于水中得到透明溶液；将溶液放置于喷雾干燥机中，在130℃下进行喷雾干燥；搜集喷出的前驱体转移到三氧化二铝坩埚中，在马弗炉中空气气氛下750℃热处理6小时，得到深棕色粉末层状氧化物材料为Na0.9Cu0.225Fe0.3Mn0.475O2，其XRD图谱与图1类似。图21为Na0.9Cu0.225Fe0.3Mn0.475O2的SEM图，从图中可以看出，该材料的颗粒尺寸平均为1微米。
将上述制备得到的层状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6。测试电压范围为2.5V～4.1V，测试结果见图22。图22中示出了第一周及第二周充放电曲线。可以看出，首周放电比容量可达101mAh/g，首周库仑效率约为76％。
实施例20
本实施例中采用前述实施例4所述的溶胶-凝胶法制备层状氧化物材料。
本实施例的具体制备步骤为，首先按化学计量比称取前驱体化合物NaNO3、Fe(NO3)3、Cu(NO3)2、Mn(C2H3O2)2分别依次溶于去离子水中，再加入适量的柠檬酸作为螯合剂，放到80℃的油浴锅中搅拌；将蒸干得到的干凝胶转移到三氧化二铝坩埚中，在200℃下，预烧2个小时；再在马弗炉中空气气氛下750℃热处理10小时，得到红棕黑色粉末的层状氧化物材料，为Na0.9Cu0.225Fe0.3Mn0.475O2，其XRD图谱与图1类似。图23为Na0.9Cu0.225Fe0.3Mn0.475O2的扫描电子显微镜(SEM)图，从图中可以看出，该材料的颗粒尺寸分布主要从500纳米到1微米。
将上述制备得到的层状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6。测试电压范围为2.5V～4.1V，测试结果见图24。图24中示出了第一周及第二周充放电曲线。可以看出，首周放电比容量可达98.6mAh/g，首周库仑效率约为79.6％，并且具有很好的循环稳定性。
实施例21
本实施例中采用前述实施例4所述的溶胶-凝胶法制备层状氧化物材料。
本实施例具体制备步骤如实施例20，但是所用前驱体化合物NaNO3、Fe(NO3)3、Cu(NO3)2、Mn(C2H3O2)2的化学计量比与实施例20中不同，得到的干凝胶再转移到三氧化二铝坩埚中，在200℃下，预烧2个小时；再在马弗炉中空气气氛下700℃热处理10小时，得到红棕黑色粉末的层状氧化物材料为Na0.9Cu0.27Fe0.3Mn0.43O2，其XRD图谱与图1类似。
将上述制备得到的层状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6。测试电压范围为2.5V～4.1V，测试结果见图25。图25中示出了第一周、第二周充放电曲线。可以看出，首周放电比容量可达98.3mAh/g，首周库仑效率约为87.8％。
实施例22
本实施例中采用前述实施例5所述的共沉淀法制备层状氧化物材料。具体包括：
按照化学计量比称取前驱物硝酸铜、硝酸铁和乙酸锰分别溶解在去离子水中；用蠕动泵管将之前配好的硝酸铜、硝酸铁和乙酸锰的水溶液缓慢的滴加到一定浓度和pH值的氨水溶液中；反应完成后将生成的沉淀取出用 去离子水洗干净，在放入80℃真空烘箱中烘干；将烘干的粉末与碳酸钠按照化学计量比均匀混合得到前驱物；再将前驱物转移到马弗炉中800℃热处理12个小时。将热处理之后的粉末研磨得到黑色层状氧化物材料为Na0.95Cu0.225Fe0.25Mn0.525O2。其XRD类似图1所示。将上述制备得到的层状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6。测试电压范围为2.5V～4.1V，首周放电比容量可达99mAh/g，首周库仑效率约为89％。
实施例23
本实施例中采用前述实施例2所述的固相法制备层状氧化物材料。
本实施例的具体制备步骤同实施例6，但所用前驱体化合物Na2CO3(分析纯)、Fe2O3、CuO、Mn2O3及MgO的化学计量与实施例6中不同，并且最终热处理温度为950℃、10小时，得到黑色粉末的层状氧化物材料为Na0.9Cu0.2Fe0.3Mn0.45Mg0.05O2，其XRD图谱类似图1。将上述制备得到的层状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6。测试电压范围为2.5V～4.1V，首周放电比容量可达96mAh/g，首周库仑效率约为90.1％。
实施例24
本实施例中采用前述实施例2所述的固相法制备层状氧化物材料。
本实施例的具体制备步骤同实施例6，但所用前驱体化合物Na2CO3(分析纯)、Fe2O3、CuO、Mn2O3及B2O3的化学计量与实施例6中不同，并且最终热处理温度为900℃、12小时，得到黑色粉末的层状氧化物材料为Na0.9Cu0.225Fe0.3Mn0.425B0.05O2，其XRD图谱类似图1。将上述制备得到的层状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6。测试电压范围为 2.5V～4.1V，首周放电比容量可达98mAh/g，首周库仑效率约为89％。
实施例25
本实施例中采用前述实施例2所述的固相法制备层状氧化物材料。
本实施例的具体制备步骤同实施例6，但所用前驱体化合物Na2CO3(分析纯)、Fe2O3、CuO、Mn2O3及Co2O3的化学计量与实施例6中不同，并且最终热处理温度为800℃、12小时，得到黑色粉末的层状氧化物材料为Na0.9Cu0.225Fe0.3Mn0.455Co0.02O2，其XRD图谱类似图1。将上述制备得到的层状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6。测试电压范围为2.5V～4.1V，首周放电比容量可达107mAh/g，首周库仑效率约为91.5％。
实施例26
本实施例中采用前述实施例2所述的固相法制备层状氧化物材料。
本实施例的具体制备步骤同实施例6，但所用前驱体化合物Na2CO3(分析纯)、Fe2O3、CuO、Mn2O3及NiO的化学计量与实施例6中不同，并且最终热处理温度为800℃、12小时，得到黑色粉末的层状氧化物材料为Na0.9Cu0.2 25 Fe0.3Mn0.425Ni0.05O2，其XRD图谱类似图1。
将上述制备得到的层状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6。测试电压范围为2.5V～4.05V，测试结果见图26。图26中示出了第一周及第二周充放电曲线。可以看出，首周放电比容量可达104.7mAh/g，首周库仑效率约为90.1％。将此材料与硬碳组装成全电池，测试电压范围为1.5V～4.05V，测试结果如图27所示，图27中显示了以C/5电流充放电的第一周和第二周曲线；可以看出首周放电比容量为307.9mAh/g(以负极活性物质质量计算)，首周库仑效率约为76％。
本发明实施例提供的层状氧化物材料制备简单，所含有的过渡金属铜、铁、锰都是无毒安全的元素，在地壳中的丰度高，因此制造成本低廉。应用本发明的层状氧化物材料的钠离子二次电池，依靠二价到三价铜变价，三价到四价铁的变价，和三价到四价锰的变价，实现比较高的首周充电容量，循环性能优异，安全性能好，具有很大实用价值，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。
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. 一种层状氧化物材料，其特征在于，所述层状氧化物材料的化学通式为：NaxCuiFejMnkMyO2+β；
    其中，M为对过渡金属位进行掺杂取代的元素，具体为Li+，Ni2+,Mg2+,Mn2+,Zn2+,Co2+,Ca2+,Ba2+,Sr2+,Mn3+,Al3+,B3+,Cr3+,Co3+,V3+,Zr4+，Ti4+,Sn4+,V4+,Mo4+,Mo5+，Ru4+，Nb5+,Si4+,Sb5+,Nb5+,Mo6+，Te6+中的一种或多种；
    所述x，y，i，j,k,β分别为对应元素所占的摩尔百分比；其中x，y，i，j,k,β之间的关系满足y+i+j+k＝1，且x+my+2i+3j+4k＝2(2+β)；其中0.8≤x≤1；0<i≤0.3；0<j≤0.5；0<k≤0.5；-0.02≤β≤0.02；m为所述M的化合价态；
    所述层状氧化物材料的空间群为R3m。
  2. 根据权利要求1所述的层状氧化物材料，其特征在于，所述层状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100wt％～108wt％的碳酸钠和所需化学计量的氧化铜、氧化铁、氧化锰和M的氧化物按比例混合成前驱体；所述M具体为Li+，Ni2+,Mg2+,Mn2+,Zn2+,Co2+,Ca2+,Ba2+,Sr2+,Mn3+,Al3+,B3+,Cr3+,Co3+,V3+,Zr4+，Ti4+,Sn4+,V4+,Mo4+,Mo5+，Ru4+，Nb5+,Si4+,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700℃～1000℃的空气气氛中热处理2～24小时；
    将热处理后的前驱体粉末进行研磨，得到所述层状氧化物材料。
  4. 一种如上述权利要求1所述的层状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100wt％～108wt％的碳酸钠和所需化学计量的氧化铜、氧化铁、氧化锰和M的氧化物按比例混合成前驱体；所述M具体为Li+，Ni2+,Mg2+,Mn2+,Zn2+,Co2+,Ca2+,Ba2+,Sr2+,Mn3+,Al3+,B3+,Cr3+,Co3+,V3+,Zr4+，Ti4+,Sn4+,V4+,Mo4+,Mo5+，Ru4+，Nb5+,Si4+,Sb5+,Nb5+,Mo6+，Te6+中的一种或多种；
    将所述前驱体加乙醇或水后搅拌均匀形成浆料；
    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650℃～1000℃的空气气氛中热处理2～24小时；
    将热处理后的前驱体粉末进行研磨，得到所述层状氧化物材料。
  5. 一种如上述权利要求1所述的层状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：
    采用化学计量比的硝酸钠、硝酸铜、硝酸铁、乙酸锰和M的硝酸盐为前驱体；所述M具体为Li+，Ni2+,Mg2+,Mn2+,Zn2+,Co2+,Ca2+,Ba2+,Sr2+,Mn3+,Al3+,B3+,Cr3+,Co3+,V3+,Zr4+，Ti4+,Sn4+,V4+,Mo4+,Mo5+，Ru4+，Nb5+,Si4+,Sb5+,Nb5+,Mo6+，Te6+中的一种或多种；
    将所述前驱体加乙醇或水后搅拌均匀形成浆料；
    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650℃～1000℃的空气气氛中热处理2～24小时；
    将热处理后的前驱体粉末进行研磨，得到所述层状氧化物材料。
  6. 一种如上述权利要求1所述的层状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100wt％～108wt％的乙酸钠或硝酸钠或碳酸钠或硫酸钠、含有铜、铁、锰、掺杂元素M的硝酸盐或硫酸盐按化学计量比溶于 水或者溶于乙醇混合成前驱体溶液；所述M具体为Li+，Ni2+,Mg2+,Mn2+,Zn2+,Co2+,Ca2+,Ba2+,Sr2+,Mn3+,Al3+,B3+,Cr3+,Co3+,V3+,Zr4+，Ti4+,Sn4+,V4+,Mo4+,Ru4+，Mo5+，Nb5+,Si4+,Sb5+,Nb5+,Mo6+，Te6+中的一种或多种；
    在50℃～100℃下搅拌，并且加入适量螯合剂，蒸干形成前驱体凝胶；
    将所述前驱体凝胶置于坩埚中，在200℃～500℃的空气气氛下，预烧2个小时；
    再在600℃～1000℃下热处理2～24小时；
    将热处理后的前驱体粉末进行研磨，得到所述层状氧化物材料。
  7. 一种如上述权利要求1所述的层状氧化物材料的制备方法，其特征在于，所述方法为共沉淀法，包括：
    将所需化学计量比的含有铜、铁、锰和M的硝酸盐或硫酸盐或碳酸盐或者氢氧化物分别溶于一定体积的去离子水中，并分别形成溶液；所述M具体为Li+，Ni2+,Mg2+,Mn2+,Zn2+,Co2+,Ca2+,Ba2+,Sr2+,Mn3+,Al3+,B3+,Cr3+,Co3+,V3+,Zr4+，Ti4+,Sn4+,V4+,Mo4+,Ru4+，Mo5+，Nb5+,Si4+,Sb5+,Nb5+,Mo6+，Te6+中的一种或多种；
    用蠕动泵将所述溶液缓慢的滴加在一定浓度和pH值的氨水溶液中，生成沉淀物；
    将得到的沉淀物用去离子水清洗干净，烘干后与碳酸钠按照化学计量比均匀混合得到的前驱物；
    将所述前驱物置于坩埚中，在600℃～1000℃的空气气氛下，热处理2～24个小时，得到前驱体粉末；
    将热处理后的前驱体粉末进行研磨，得到所述层状氧化物材料。
  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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