CN116145154A - Phosphate sodium ion battery positive electrode material and preparation method thereof - Google Patents

Phosphate sodium ion battery positive electrode material and preparation method thereof Download PDF

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Publication number
CN116145154A
CN116145154A CN202211625045.9A CN202211625045A CN116145154A CN 116145154 A CN116145154 A CN 116145154A CN 202211625045 A CN202211625045 A CN 202211625045A CN 116145154 A CN116145154 A CN 116145154A
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ion battery
sodium ion
commercial
positive electrode
aluminum
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唐怀远
王真
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Shandong Runya Nanon New Energy Technology Co ltd
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Shandong Runya Nanon New Energy Technology Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/14—Alkali metal compounds
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B25/00—Phosphorus; Compounds thereof
    • C01B25/16—Oxyacids of phosphorus; Salts thereof
    • C01B25/26—Phosphates
    • C01B25/45—Phosphates containing plural metal, or metal and ammonium
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/50—Processes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/30—Three-dimensional structures
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/40—Electric properties
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The embodiment of the invention discloses a phosphate sodium ion battery anode material and a preparation method thereof, and more particularly relates to an olivine-type NaFe x Mn y PO 4 A positive electrode material of sodium ion battery and its preparation method. The preparation method comprises the following steps: the method comprises the steps of taking a commercial phosphate lithium battery anode material as an active substance, preparing an electrode through a pressing block, loading the electrode into an electrolytic cell, removing lithium through an electrochemical method, and then inserting sodium ions through the electrochemical method. The phosphate sodium ion battery anode material provided by the invention has excellent electrochemical performance, and meanwhile, the source of raw materials is richThe method has the advantages of simple process, low energy consumption, green and environment-friendly performance, and can be applied to mass production.

Description

Phosphate sodium ion battery positive electrode material and preparation method thereof
Technical Field
The invention belongs to the technical field of sodium ion batteries, in particular relates to a phosphate sodium ion battery anode material and a preparation method thereof, and more particularly relates to an olivine type NaFe x Mn y PO 4 A positive electrode material of sodium ion battery and its preparation method.
Background
In recent years, with the increasing exhaustion of fossil energy and the increasing severity of environmental problems such as global warming, new energy related research has received widespread attention in society. With the progress of battery industry technology, the demand of the battery industry is also continuously increased; the lithium ion battery is widely used on electric automobiles, and the lithium ion battery is widely used on energy storage equipment. However, due to the scarcity of the related active material resources of the lithium ion battery, the battery cost is always high, and meanwhile, the serious problems of related resource exhaustion and the like are faced. Along with the development of lithium resources and noble metals such as nickel, cobalt and the like, the production cost of the lithium ion battery is continuously increased, and the popularization and the application of new energy vehicles and battery energy storage markets are severely restricted. The solution of battery technology with abundant resources, low cost, environmental protection and safety is still the primary solution.
The working principle of the sodium ion battery and the lithium ion battery is basically similar, sodium element is one of metal elements stored in the crust, and materials used by the sodium ion battery can be low-cost and easily-obtained, so that the sodium ion battery is one of the most development potential technologies. However, the specific energy of the sodium ion battery is lower than that of the lithium ion battery, so that the improvement of the specific energy of the sodium ion battery is a technical problem which needs to be solved at present, and the problem which needs to be solved first for solving the problems of popularization and application of new energy vehicles and battery energy storage.
The main positive electrode materials of the sodium ion secondary batteries are mainly divided into: layered transition metal oxides, prussian blue, and polyanionic materials. The layered transition metal oxide has low reversible capacity, contains noble metals such as copper, nickel and the like, has high cost, is sensitive to moisture and is difficult to apply in large scale. Prussian blue compounds have the disadvantages of low compaction density and poor thermal stability, and toxic CN exists in the materials - A group.
Olivine-type LiFe of positive electrode material containing iron or manganese x Mn y PO 4 (x+y=1) as a positive electrode material for lithium ion batteries, has been used in a large scale. NaFePO 4 And NaMnPO 4 There are mainly two crystalline forms, marisite and olivine. marisite type NaFePO 4 And NaMnPO 4 As a sodium ion positive electrodeThe material is inactive and, at present, naFePO is obtained by conventional synthetic methods 4 And NaMnPO 4 Is marilite crystal form, olivin crystal form NaFePO 4 With NaMnPO 4 Active but difficult to synthesize. Thus, a simple process is provided for preparing the olivin crystal form NaFePO 4 With NaMnPO 4 It is significant.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention provides a method for rapidly preparing olivine-type NaFe by using a commercial phosphate lithium battery anode material x Mn y PO 4 (x+y=1, 0.ltoreq.x.ltoreq.1, 0.ltoreq.y.ltoreq.1) sodium ion battery positive electrode material.
In order to achieve the above object, the embodiment of the present invention provides the following technical solutions:
according to a first aspect of an embodiment of the present invention, the present invention provides an olivine-type NaFe x Mn y PO 4 The preparation method of the positive electrode material of the sodium ion battery comprises the steps of (x+y=1, x is more than or equal to 0 and less than or equal to 1, y is more than or equal to 0 and less than or equal to 1), preparing an electrode by using a commercial phosphate lithium battery positive electrode material as an active substance through a briquetting, loading the electrode into an electrolytic cell, removing lithium by an electrochemical method, and then embedding sodium ions by the electrochemical method.
In some specific embodiments, the method comprises the steps of:
(1) Mixing a commercial phosphate lithium battery anode material with a conductive agent, placing the mixture and a current collector into a mold, and pressing to obtain an active material block;
(2) Vacuum drying the active material block prepared in the step (1) at 100-150 ℃ for 5-24 h;
(3) The metal lithium is used as an anode, the active material block is used as a cathode, and the cathode, the commercial lithium ion battery electrolyte and the diaphragm are assembled together to form an electrolytic cell;
(4) Constant-current voltage-limiting charging is carried out on the electrolytic cell assembled in the step (3) at a rate of 0.05-1C (calculated by the capacity of the positive electrode active material);
(5) Taking out the active material blocks after the charging in the step (4), cleaning and drying;
(6) In a drying room, taking metal sodium as an anode, taking the active substance block in the step (5) as a cathode, and assembling the active substance block with commercial sodium ion battery electrolyte and a diaphragm together to form an electrolytic cell;
(7) Performing constant-current voltage-limiting discharge on the electrolytic cell assembled in the step (6) at a multiplying power of 0.01-1C;
(8) Taking out the active material block after discharging in the step (7), cleaning, drying, crushing and sieving to obtain the olivine-type NaFe x Mn y PO 4 (x+y=1, 0.ltoreq.x.ltoreq.1, 0.ltoreq.y.ltoreq.1) sodium ion battery positive electrode material.
Further, in the step (1), the commercial lithium phosphate battery positive electrode material is one or more of a commercial lithium iron phosphate material or a commercial lithium manganese iron phosphate material; the mass ratio of the commercial phosphate lithium battery anode material to the conductive agent is (80-99) that is (1-20); the conductive agent is selected from one or more of conductive graphite, conductive carbon black, graphene and carbon nanotubes.
Further, in the step (1), the current collector is made of an aluminum material and is selected from one or more of an aluminum plate, an aluminum net, an aluminum rod, an aluminum needle, an aluminum woven net, an aluminum punching plate, an aluminum foil and an aluminum belt; the pressing pressure is 20 Mpa-200 Mpa; the thickness of the active material block is 0.5 mm-10 mm.
Further, steps (3) to (8) are carried out in a drying room or a glove box; the dew point of the drying room is less than or equal to-45 ℃, the temperature is 20-25 ℃, and the cleanliness is less than or equal to 10 ten thousand grades.
Further, in the step (4), the limiting voltage of the constant-current voltage-limiting charging is 3.6V-4.3V; in the step (7), the limiting voltage of the constant-current voltage limiting discharge is 0.5V-1.5V.
Further, the organic solvent used for the washing is selected from one or more of DMC, EMC, PC, DEC.
Further, the drying is carried out in a vacuum box, the drying temperature is 100-150 ℃ and the drying time is 5-24 hours.
Further, in the step (8), the number of the sieves is 300-600 mesh.
According to a second aspect of embodiments of the invention, the inventionProvides an olivine-type NaFe x Mn y PO 4 (x+y=1, 0.ltoreq.x.ltoreq.1, 0.ltoreq.y.ltoreq.1) sodium ion battery positive electrode material, which is produced by the method as described above.
The embodiment of the invention has the following advantages:
first: compared with the prior art, the method takes the mass produced lithium iron phosphate material or lithium manganese iron phosphate material as the raw material, and produces the sodium ion battery anode material by an electrochemical method, so that the method has the advantages of abundant raw material sources and simple process, and is a technology capable of mass production.
Second,: naFe provided by the invention x Mn y PO 4 The anode material has an olivine structure, and has excellent electrochemical performance as an anode material of a sodium ion battery, and the discharge gram capacity of the anode material is more than or equal to 140mAh/g at 0.1C, which is very beneficial to improving the specific energy of the sodium ion battery and popularizing the application of the sodium ion battery.
Third,: the preparation process does not need high-temperature heat treatment, and is a low-energy-consumption and environment-friendly production technology.
Fourth,: the material prepared by the invention can be used for referencing the lithium iron phosphate material in application, can adopt a mature battery manufacturing technology, does not need to develop a new process, and has important significance for quick marketization.
Fifth,: the material prepared by the invention has the cycle life close to that of the lithium iron phosphate material, and the service life can reach more than 5000 times, so that the material can be applied to large-scale electrochemical energy storage.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below. It will be apparent to those of ordinary skill in the art that the drawings in the following description are exemplary only and that other implementations can be obtained from the extensions of the drawings provided without inventive effort.
FIG. 1 is a discharge graph of example 1;
fig. 2 is a cycle life graph of example 1.
Detailed Description
Other advantages and advantages of the present invention will become apparent to those skilled in the art from the following detailed description, which, by way of illustration, is to be read in connection with certain specific embodiments, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
The positive electrode material of the sodium ion battery is prepared by an electrochemical method, and the method comprises the following steps:
the first step: 5000g of commercial LiFe was weighed out 0.5 Mn 0.5 PO 4 The lithium battery anode material is mixed with 50g of conductive graphite, an aluminum mesh is taken as a current collector and put into a die, and an active material block with the thickness of 4mm is pressed under the pressure of 50 Mpa.
And a second step of: the active mass prepared in the first step was dried in vacuo at 100℃for 8h.
And a third step of: in a drying room, under the conditions of dew point of-50 ℃, temperature of 25 ℃ and cleanliness of 1 ten thousand grades, metal lithium is used as an anode, an active substance block is used as a cathode, and the metal lithium, the commercial lithium ion battery electrolyte and a diaphragm are assembled together to form the electrolytic cell.
Fourth step: and (3) carrying out constant-current voltage-limiting charging on the electrolytic cell assembled in the third step by using an electrochemical method at a current of 37.5A and a limiting voltage of 4.2V.
Fifth step: and (3) taking out the active substance blocks after the charging in the fourth step, cleaning for 5 times by using DMC organic solvent, and then putting the active substance blocks into a drying box for drying.
Sixth step: in a drying room, under the conditions of dew point of-50 ℃, temperature of 25 ℃ and cleanliness of 1 ten thousand grades, the metal sodium is taken as an anode, the active substance block in the fifth step is taken as a cathode, and the anode, the commercial sodium ion battery electrolyte and a diaphragm are assembled together to form the electrolytic cell.
Seventh step: the cell in the sixth step was discharged at a current of 37.7A, and the limiting voltage was 1V.
Eighth step: taking out the active substance blocks after discharging in the seventh step, cleaning for 5 times by DMC organic solvent, then placing the active substance blocks into a vacuum drying box, vacuum drying for 12 hours at 115 ℃, and then crushing and sieving the active substance blocks to obtain the olivine type NaFe 0.5 Mn 0.5 PO 4 And a positive electrode material.
The material prepared in example 1 was ball-milled and then used to prepare a positive electrode sheet of a sodium ion secondary battery. The method comprises the following specific steps: the material of example 1, acetylene black and binder polyvinylidene fluoride (PVDF) were mixed in a mass ratio of 85:10:5 by NMP solvent, and the mixed slurry was coated on aluminum foil and dried under vacuum at 120℃for 10 hours. The simulated button cell is carried out in a glove box of Ar gas, a counter electrode adopts metallic sodium, an electrolyte adopts commercial sodium ion battery electrolyte, a CR2032 cell is assembled, the tested voltage range is between 1.5 and 3.6V, the initial charge specific capacity is 158mAh/g, the discharge specific capacity is 145mAh/g and the initial effect of the cell is 91.7 percent under the multiplying power of C/10, and the results are shown in table 1. The material obtained in example 1 was measured under 100MPa using a powder compaction density tester, and the compaction density was 2.53g/cm 3 The results are shown in Table 2.
The material prepared in the example 1, PVDF, carbon tube and NMP are prepared into 18650 type cylindrical battery positive plate according to the manufacturing process of 18650 type battery positive plate.
The preparation method comprises the steps of taking hard carbon material and carbon tube, styrene-butadiene rubber and CMC, and preparing the 18650 type cylindrical battery negative electrode plate according to a 18650 type battery negative electrode plate manufacturing process.
The separator was a commercial polyethylene separator.
The electrolyte is a mixture of commercial sodium ion battery electrolyte.
The positive electrode, the negative electrode, the electrolyte and the separator prepared in the embodiment 1 are prepared into 18650 batteries according to the assembly process of the 18650 batteries, and the tested voltage ranges from 1.5V to 3.6V.
The prepared batteries were respectively subjected to 1C discharge, and a discharge graph of the battery 1C is shown in fig. 1.
The battery cycle performance test is carried out, and the test method comprises the following steps: at the temperature of 25 ℃,
constant current and constant voltage of 1C to upper limit voltage of 3.6V, standing for 10min;
discharging the 1C constant current to the lower limit voltage of 1.5V, and standing for 10min;
repeating the process for 5000 times;
the results are shown in FIG. 2.
Example 2
The positive electrode material of the sodium ion battery is prepared by an electrochemical method, and the method comprises the following steps:
the first step: 1000g of commercial LiFePO were weighed out 4 The lithium battery positive electrode material was mixed with 20g of carbon black, and an aluminum plate was put into a mold together as a current collector, and pressed into an active material block having a thickness of 3mm under a pressure of 20 Mpa.
And a second step of: the active mass prepared in the first step was dried in vacuo at 100℃for 12h.
And a third step of: in a drying room, under the conditions of dew point of 65 ℃ below zero, temperature of 25 ℃ and cleanliness of 1 ten thousand grades, metal lithium is used as an anode, an active substance block is used as a cathode, and the metal lithium, the commercial lithium ion battery electrolyte and a diaphragm are assembled together to form the electrolytic cell.
Fourth step: and (3) carrying out constant-current voltage-limiting charging on the electrolytic cell assembled in the third step by using an electrochemical method at a current of 1.5A and a limiting voltage of 3.6V.
Fifth step: and (3) taking out the active substance blocks after the charging in the fourth step, cleaning for 5 times by using EMC organic solvent, and then putting the active substance blocks into a drying box for drying.
Sixth step: in a drying room, under the conditions of dew point-65 ℃, temperature 25 ℃ and cleanliness of 1 ten thousand grades, the metal sodium is taken as an anode, the active material block in the fifth step is taken as a cathode, and the anode, the commercial sodium ion battery electrolyte and a diaphragm are assembled together to form the electrolytic cell.
Seventh step: the cell in the sixth step was discharged at a current of 3A, and the limiting voltage was 1V.
Eighth step: taking out the active material block after discharging in the seventh step, and using EMC organic solvent for carrying outWashing for 5 times, then placing into a vacuum drying box, vacuum drying for 8 hours at 120 ℃, and then crushing and sieving to obtain the olivine-type NaFePO of the invention 4 And a positive electrode material.
The material prepared in example 2 was ball-milled and then used to prepare a positive electrode sheet of a sodium ion secondary battery. The method comprises the following specific steps: the material of example 2, acetylene black and binder polyvinylidene fluoride (PVDF) were mixed in a mass ratio of 85:10:5 by NMP solvent, and the mixed slurry was coated on aluminum foil and dried under vacuum at 120℃for 10 hours. The simulated button cell is carried out in a glove box of Ar gas, a counter electrode adopts metallic sodium, an electrolyte adopts commercial sodium ion battery electrolyte, a CR2032 cell is assembled, the tested voltage range is between 1.5 and 3.6V, the initial charge specific capacity is 153.7mAh/g, the discharge specific capacity is 143mAh/g under the multiplying power of C/10, and the initial effect of the cell is 93%, and the results are shown in Table 1. The material obtained in example 2 was measured under 100MPa using a powder compaction density tester, and the compaction density was 2.60g/cm 3 The results are shown in Table 2.
Example 3
The positive electrode material of the sodium ion battery is prepared by an electrochemical method, and the method comprises the following steps:
the first step: 10000g of commercial LiFe are weighed 0.7 Mn 0.3 PO 4 The lithium battery anode material and 100g of carbon nano-tubes are mixed, an aluminum plate current collector is put into a die together, and an active material block with the thickness of 6mm is pressed under the pressure of 30 Mpa.
And a second step of: the active mass prepared in the first step was dried in vacuo at 100℃for 8h.
And a third step of: in a drying room, under the conditions of dew point of-60 ℃, temperature of 25 ℃ and cleanliness of 1 ten thousand grades, metal lithium is used as an anode, an active substance block is used as a cathode, and the metal lithium, the commercial lithium ion battery electrolyte and a diaphragm are assembled together to form the electrolytic cell.
Fourth step: and (3) carrying out constant-current voltage-limiting charging on the electrolytic cell assembled in the third step by using an electrochemical method at a current of 30A and a limiting voltage of 4.2V.
Fifth step: and (3) taking out the active substance blocks after the charging in the fourth step, cleaning for 5 times by using a PC organic solvent, and then putting the active substance blocks into a drying box for drying.
Sixth step: in a drying room, under the conditions of dew point of-60 ℃, temperature of 25 ℃ and cleanliness of 1 ten thousand grades, the metal sodium is taken as an anode, the active substance block in the fifth step is taken as a cathode, and the anode, the commercial sodium ion battery electrolyte and a diaphragm are assembled together to form the electrolytic cell.
Seventh step: the cell in the sixth step was discharged at a current of 30A with a limiting voltage of 1V.
Eighth step: taking out the active substance blocks after discharging in the seventh step, washing for 5 times by using PC organic solvent, then placing the active substance blocks into a vacuum drying box, vacuum drying for 18 hours at 108 ℃, and then crushing and sieving the active substance blocks to obtain the olivine-type NaFe 0.7 Mn 0.3 PO 4 And a positive electrode material.
The material prepared in example 3 was ball-milled and then used to prepare a positive electrode sheet of a sodium ion secondary battery. The method comprises the following specific steps: the material of example 3, acetylene black and binder polyvinylidene fluoride (PVDF) were mixed in a mass ratio of 85:10:5 by NMP solvent, and the mixed slurry was coated on aluminum foil and dried under vacuum at 120℃for 10 hours. The simulated button cell is carried out in a glove box of Ar gas, a counter electrode adopts metallic sodium, an electrolyte adopts commercial sodium ion battery electrolyte, a CR2032 cell is assembled, the tested voltage range is between 1.5 and 3.6V, the initial charge specific capacity is 156mAh/g, the discharge specific capacity is 141mAh/g under the multiplying power of C/10, and the initial effect of the cell is 90.4%, and the results are shown in Table 1. The material obtained in example 3 was measured under 100MPa using a powder compaction density tester, and the compaction density was 2.56g/cm 3 The results are shown in Table 2.
Example 4
The positive electrode material of the sodium ion battery is prepared by an electrochemical method, and the method comprises the following steps:
the first step: 3000g of commercial LiFe was weighed out 0.3 Mn 0.7 PO 4 The lithium battery anode material is mixed with 30g of graphene, and an aluminum strip is taken as a current collector to be put togetherAnd (3) putting the mixture into a die, and pressing the mixture into an active substance block with the thickness of 4mm under the pressure of 50 Mpa.
And a second step of: the active mass prepared in the first step was dried in vacuo at 108℃for 8h.
And a third step of: in a drying room, under the conditions of dew point of-50 ℃, temperature of 25 ℃ and cleanliness of 10 ten thousand grades, metal lithium is used as an anode, an active substance block is used as a cathode, and the metal lithium, the commercial lithium ion battery electrolyte and a diaphragm are assembled together to form the electrolytic cell.
Fourth step: and (3) carrying out constant-current voltage-limiting charging on the electrolytic cell assembled in the third step by an electrochemical method at a current of 18A and a limiting voltage of 4.3V.
Fifth step: and (3) taking out the active substance blocks after the charging in the fourth step, cleaning for 5 times by using a DEC organic solvent, and then putting the active substance blocks into a drying box for drying.
Sixth step: in a drying room, under the conditions of dew point of-50 ℃, temperature of 25 ℃ and cleanliness of 10 ten thousand grades, the metal sodium is taken as an anode, the active substance block in the fifth step is taken as a cathode, and the anode, the commercial sodium ion battery electrolyte and a diaphragm are assembled together to form the electrolytic cell.
Seventh step: the cell in the sixth step was discharged at 18A current with a limiting voltage of 1V.
Eighth step: taking out the active substance blocks after discharging in the seventh step, washing for 5 times by using a DEC organic solvent, then placing the active substance blocks into a vacuum drying box, vacuum drying for 15 hours at 100 ℃, and then crushing and sieving the active substance blocks to obtain the olivine-type NaFe 0.3 Mn 0.7 PO 4 And a positive electrode material.
The material prepared in example 4 was ball-milled and then used to prepare a positive electrode sheet of a sodium ion secondary battery. The method comprises the following specific steps: the material of example 4, acetylene black and binder polyvinylidene fluoride (PVDF) were mixed in a mass ratio of 85:10:5 by NMP solvent, and the mixed slurry was coated on aluminum foil and dried under vacuum at 120℃for 10 hours. The simulated button cell was carried out in an Ar glove box, the counter electrode was sodium metal, the electrolyte was commercial sodium ion battery electrolyte, and a CR2032 cell was assembled, and testedThe voltage range of (2) is 1.5-3.6V, the initial charge specific capacity is 158mAh/g, the discharge specific capacity is 142mAh/g, and the initial efficiency of the battery is 89.9% under the multiplying power of C/10, and the result is shown in Table 1. The material obtained in example 4 was measured under 100MPa using a powder compaction density tester, and the compaction density was 2.49g/cm 3 The results are shown in Table 2.
Example 5
The positive electrode material of the sodium ion battery is prepared by an electrochemical method, and the method comprises the following steps:
the first step: 4000g of commercial LiFe are weighed out 0.4 Mn 0.6 PO 4 The lithium battery anode material is mixed with 100g of carbon black, an aluminum woven mesh is taken as a current collector and put into a die, and an active material block with the thickness of 3mm is pressed under the pressure of 35 Mpa.
And a second step of: the active mass prepared in the first step was dried in vacuo at 100℃for 8h.
And a third step of: in a drying room, under the conditions of dew point of-55 ℃, temperature of 25 ℃ and cleanliness of 1 ten thousand grades, metal lithium is used as an anode, an active substance block is used as a cathode, and the metal lithium, the commercial lithium ion battery electrolyte and a diaphragm are assembled together to form the electrolytic cell.
Fourth step: and (3) carrying out constant-current voltage-limiting charging on the electrolytic cell assembled in the third step by using an electrochemical method at a current of 37.5A and a limiting voltage of 4.2V.
Fifth step: and (3) taking out the active substance blocks after the charging in the fourth step, cleaning for 5 times by using DMC organic solvent, and then putting the active substance blocks into a drying box for drying.
Sixth step: in a drying room, under the conditions of dew point of-55 ℃, temperature of 25 ℃ and cleanliness of 1 ten thousand grades, the metal sodium is taken as an anode, the active substance block in the fifth step is taken as a cathode, and the anode, the commercial sodium ion battery electrolyte and a diaphragm are assembled together to form the electrolytic cell.
Seventh step: the cell in the sixth step was discharged at a current of 37.7A, and the limiting voltage was 1V.
Eighth step: taking out the active material block after discharging in the seventh step, cleaning for 5 times by DMC organic solvent, and then placing into a vacuum drying boxVacuum drying at 110deg.C for 17 hr, pulverizing, sieving to obtain the olivine-type NaFe 0.4 Mn 0.6 PO 4 And a positive electrode material.
The material prepared in example 5 was ball-milled and then used to prepare a positive electrode sheet of a sodium ion secondary battery. The method comprises the following specific steps: the material of example 5, acetylene black and binder polyvinylidene fluoride (PVDF) were mixed in a mass ratio of 85:10:5 by NMP solvent, and the mixed slurry was coated on aluminum foil and dried under vacuum at 120℃for 10 hours. The simulated button cell is carried out in a glove box of Ar gas, a counter electrode adopts metallic sodium, an electrolyte adopts commercial sodium ion battery electrolyte, a CR2032 cell is assembled, the tested voltage range is between 1.5 and 3.6V, the initial charge specific capacity is 156mAh/g, the discharge specific capacity is 144mAh/g and the initial effect of the cell is 92.3% under the multiplying power of C/10, and the results are shown in Table 1. The material obtained in example 5 was measured under 100MPa using a powder compaction density tester, and the compaction density was 2.52g/cm 3 The results are shown in Table 2.
Example 6
The positive electrode material of the sodium ion battery is prepared by an electrochemical method, and the method comprises the following steps:
the first step: 6000g of commercial LiFe was weighed out 0.6 Mn 0.4 PO 4 The lithium battery anode material is mixed with 80g of graphene, an aluminum punching plate is taken as a current collector and put into a die together, and an active material block with the thickness of 4mm is pressed under the pressure of 50 Mpa.
And a second step of: the active mass prepared in the first step was dried in vacuo at 100℃for 8h.
And a third step of: in a drying room, under the conditions of dew point of-50 ℃, temperature of 25 ℃ and cleanliness of 1 ten thousand grades, metal lithium is used as an anode, an active substance block is used as a cathode, and the metal lithium, the commercial lithium ion battery electrolyte and a diaphragm are assembled together to form the electrolytic cell.
Fourth step: and (3) carrying out constant-current voltage-limiting charging on the electrolytic cell assembled in the third step by using an electrochemical method at a current of 37.5A and a limiting voltage of 4.2V.
Fifth step: and (3) taking out the active substance blocks after the charging in the fourth step, cleaning for 5 times by using DMC organic solvent, and then putting the active substance blocks into a drying box for drying.
Sixth step: in a glove box, under the environment of oxygen less than 1ppm and moisture less than ppm, the metal sodium is taken as an anode, the active material block in the fifth step is taken as a cathode, and the anode, the commercial sodium ion battery electrolyte and a diaphragm are assembled together to form an electrolytic cell.
Seventh step: the cell in the sixth step was discharged at a current of 37.7A, and the limiting voltage was 1V.
Eighth step: taking out the active substance blocks after discharging in the seventh step, cleaning for 5 times by DMC organic solvent, then placing the active substance blocks into a vacuum drying box, vacuum drying for 12 hours at 120 ℃, and then crushing and sieving the active substance blocks to obtain the olivine type NaFe 0.6 Mn 0.4 PO 4 And a positive electrode material.
The material prepared in example 6 was ball-milled and then used to prepare a positive electrode sheet of a sodium ion secondary battery. The method comprises the following specific steps: the material of example 6, acetylene black and binder polyvinylidene fluoride (PVDF) were mixed in a mass ratio of 85:10:5 by NMP solvent, and the mixed slurry was coated on aluminum foil and dried under vacuum at 120℃for 10 hours. The simulated button cell is carried out in a glove box of Ar gas, a counter electrode adopts metallic sodium, an electrolyte adopts commercial sodium ion battery electrolyte, a CR2032 cell is assembled, the tested voltage range is between 1.5 and 3.6V, the initial charge specific capacity is 160mAh/g, the discharge specific capacity is 147mAh/g and the initial effect of the cell is 91.9 percent under the multiplying power of C/10, and the results are shown in table 1. The material obtained in example 6 was measured under 100MPa using a powder compaction density tester, and the compaction density was 2.54g/cm 3 The results are shown in Table 2.
Comparative example 1
Commercial Prussian blue sodium ion battery material (Na 2 Fe Fe(CN) 6 ) The method is used for manufacturing the positive electrode plate of the sodium ion secondary battery. The method comprises the following specific steps: na is mixed with 2 Fe Fe(CN) 6 The powder was mixed with acetylene black and a binder polyvinylidene fluoride (PVDF) in a mass ratio of 85:10:5 by means of NMP solventMixing, coating the mixed slurry on aluminum foil, and drying at 120 ℃ for 24 hours under vacuum condition for standby. The simulated button cell is carried out in an Ar glove box, a counter electrode adopts metallic sodium, an electrolyte adopts commercial sodium ion battery electrolyte, the CR2032 cell is assembled, the tested voltage range is between 1.5 and 4.0V, the initial charge specific capacity is 150mAh/g, the discharge specific capacity is 128mAh/g and the initial effect of the cell is 85.3 percent under the multiplying power of C/10. The material obtained in comparative example 1 was measured under 100MPa using a powder compaction density tester, and the compaction density was 1.51g/cm 3 。
It can be seen that the positive electrode material provided in the examples of the present invention has a gram capacity superior to that of Na in the prior art when used in a sodium ion secondary battery 2 Fe Fe(CN) 6 And a positive electrode material. At the same time Na 2 Fe Fe(CN) 6 Contains toxic (CN) - The material is environment-friendly, and the iron element in the material is cheap and easy to obtain, is environment-friendly, so that the material can be popularized and applied on a large scale.
Comparative example 2
Commercial sodium vanadium phosphate Na 3 V 2 (PO 4 ) 3 The material is used for preparing the positive electrode plate of the sodium ion secondary battery. The method comprises the following specific steps: na is mixed with 3 V 2 (PO 4 ) 3 Mixing the powder with acetylene black and a binder polyvinylidene fluoride (PVDF) according to a mass ratio of 85:10:5 by an NMP solvent, coating the mixed slurry on an aluminum foil, and drying at 120 ℃ for 24 hours under vacuum condition for standby. The simulated button cell is carried out in a glove box of Ar gas, a counter electrode adopts metallic sodium, an electrolyte adopts commercial sodium ion battery electrolyte, the CR2032 cell is assembled, the tested voltage range is between 2.0 and 4.0V, the initial charge specific capacity is 115mAh/g, the discharge specific capacity is 90mAh/g and the initial effect of the cell is 78.2 percent under the multiplying power of C/10. The material obtained in comparative example 1 was measured under 100MPa using a powder compaction density tester, and the compaction density was measured to be 2.10g/cm 3 。
It can be seen that the positive electrode material provided in the examples of the present invention, when used in a sodium ion secondary battery, was defined asThe capacity is superior to Na in the prior art 3 V 2 (PO 4 ) 3 And a positive electrode material. Meanwhile, the iron in the material is cheap and easy to obtain, and the cost is lower than that of the vanadium material, so that the material can be popularized and applied on a large scale.
Table 1 comparative table of electrical properties of examples and comparative examples
Figure BDA0004003937350000121
Figure BDA0004003937350000131
Table 2 comparison of the compacted densities of examples and comparative examples
Density of compaction at 100MPa (g/cm) 3 )
Example 1 2.53
Example 2 2.60
Example 3 2.56
Example 4 2.49
Example 5 2.52
Example 6 2.54
Comparative example 1 1.51
Comparative example 2 2.10
By comparing examples with comparative examples, it can be concluded that: the technical scheme of the invention has outstanding superiority and is mainly characterized in that:
1. the material is far higher than Prussian blue sodium ion battery material and vanadium sodium phosphate material in gram capacity and first effect, and is suitable for developing sodium ion batteries with high specific energy;
2. the compaction density of the material is far higher than that of Prussian blue sodium ion battery material and vanadium sodium phosphate material, and is equivalent to that of commercial lithium iron phosphate material, so that the volume energy density of the sodium ion battery can be improved.
While the invention has been described in detail in the foregoing general description and specific examples, it will be apparent to those skilled in the art that modifications and improvements can be made thereto. Accordingly, such modifications or improvements may be made without departing from the spirit of the invention and are intended to be within the scope of the invention as claimed.

Claims (10)

1. Olivine type NaFe x Mn y PO 4 The preparation method of the positive electrode material of the sodium ion battery is characterized in that the positive electrode material of the commercial phosphate lithium battery is used as an active substance, an electrode is prepared through a briquetting, the electrode is filled into an electrolytic cell, lithium is removed through an electrochemical method, and then sodium ions are intercalated through an electrochemical method.
2. The method of preparation according to claim 1, characterized in that it comprises the steps of:
(1) Mixing a commercial phosphate lithium battery anode material with a conductive agent, placing the mixture and a current collector into a mold, and pressing to obtain an active material block;
(2) Vacuum drying the active material block prepared in the step (1) at 100-150 ℃ for 5-24 h;
(3) The metal lithium is used as an anode, the active material block is used as a cathode, and the cathode, the commercial lithium ion battery electrolyte and the diaphragm are assembled together to form an electrolytic cell;
(4) Constant-current voltage-limiting charging is carried out on the electrolytic cell assembled in the step (3) at a rate of 0.05-1C (calculated by the capacity of the positive electrode active material);
(5) Taking out the active material blocks after the charging in the step (4), cleaning and drying;
(6) In a drying room, taking metal sodium as an anode, taking the active substance block in the step (5) as a cathode, and assembling the active substance block with commercial sodium ion battery electrolyte and a diaphragm together to form an electrolytic cell;
(7) Performing constant-current voltage-limiting discharge on the electrolytic cell assembled in the step (6) at a multiplying power of 0.01-1C;
(8) Taking out the active material block after discharging in the step (7), cleaning, drying, crushing and sieving to obtain the olivine-type NaFe x Mn y PO 4 (x+y=1, 0.ltoreq.x.ltoreq.1, 0.ltoreq.y.ltoreq.1) sodium ion battery positive electrode material.
3. The process according to claim 2, wherein in step (1),
the commercial phosphate lithium battery anode material is one or more of commercial lithium iron phosphate materials or commercial lithium manganese iron phosphate materials;
the mass ratio of the commercial phosphate lithium battery anode material to the conductive agent is (80-99) that is (1-20);
the conductive agent is selected from one or more of conductive graphite, conductive carbon black, graphene and carbon nanotubes.
4. The process according to claim 2, wherein in step (1),
the current collector is made of aluminum material and is selected from one or more of aluminum plates, aluminum meshes, aluminum rods, aluminum needles, aluminum woven meshes, aluminum punching plates, aluminum foils and aluminum strips;
the pressing pressure is 20 Mpa-200 Mpa;
the thickness of the active material block is 0.5 mm-10 mm.
5. The method according to claim 2, wherein steps (3) to (8) are carried out in a drying room or a glove box;
the dew point of the drying room is less than or equal to-45 ℃, the temperature is 20-25 ℃, and the cleanliness is less than or equal to 10 ten thousand grades.
6. The method according to claim 2, wherein,
in the step (4), the limiting voltage of the constant-current voltage-limiting charging is 3.6V-4.3V;
in the step (7), the limiting voltage of the constant-current voltage limiting discharge is 0.5V-1.5V.
7. The method according to claim 2, wherein,
the organic solvent used for the washing is selected from one or more of DMC, EMC, PC, DEC.
8. The method according to claim 2, wherein,
the drying is carried out in a vacuum box, the drying temperature is 100-150 ℃ and the drying time is 5-24 h.
9. The method according to claim 2, wherein,
in the step (8), the number of the sieves is 300-600 meshes.
10. Olivine type NaFe x Mn y PO 4 (x+y=1, 0.ltoreq.x.ltoreq.1, 0.ltoreq.y.ltoreq.1) sodium ion battery positive electrodeMaterial, characterized in that it is made by the method according to any one of claims 1-9.
CN202211625045.9A 2022-12-16 2022-12-16 Phosphate sodium ion battery positive electrode material and preparation method thereof Pending CN116145154A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116779778A (en) * 2023-08-11 2023-09-19 深圳海辰储能控制技术有限公司 Positive electrode plate, preparation method thereof, energy storage device and power utilization device

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116779778A (en) * 2023-08-11 2023-09-19 深圳海辰储能控制技术有限公司 Positive electrode plate, preparation method thereof, energy storage device and power utilization device
CN116779778B (en) * 2023-08-11 2024-02-09 深圳海辰储能控制技术有限公司 Positive electrode plate, preparation method thereof, energy storage device and power utilization device

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