CN107017395A - A kind of carbon coating manganese pyrophosphate sodium@graphene oxide composite materials with sandwich structure and its preparation method and application - Google Patents

A kind of carbon coating manganese pyrophosphate sodium@graphene oxide composite materials with sandwich structure and its preparation method and application Download PDF

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Publication number
CN107017395A
CN107017395A CN201710365046.7A CN201710365046A CN107017395A CN 107017395 A CN107017395 A CN 107017395A CN 201710365046 A CN201710365046 A CN 201710365046A CN 107017395 A CN107017395 A CN 107017395A
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sodium
manganese
carbon coating
graphene oxide
sandwich structure
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CN107017395B (en
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张治安
赖延清
李煌旭
尚国志
陈晓彬
肖志伟
张凯
李劼
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Hunan Nabang New Energy Co ltd
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Central South University
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • 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 invention discloses a kind of carbon coating manganese pyrophosphate sodium@graphene oxide composite materials with sandwich structure and its preparation method and application, the graphene oxide sheet that the composite is evenly distributed with carbon coating manganese pyrophosphate sodium particle by surface, which is stacked, to be constituted.Added in the aqueous solution dissolved with phosphorus source, sodium source, manganese source and complexing agent after graphene oxide, ultrasonically treated, liquid nitrogen frozen and freeze-drying are carried out successively, presoma is obtained；The presoma is placed under protective atmosphere; it is heat-treated; produce the carbon coating manganese pyrophosphate sodium@graphene oxide composite materials with sandwich structure; it has excellent chemical property as sodium-ion battery positive material; and " Na Mn P O " system aboundresources; it is with low cost, and the preparation method is simple to operate, commercial application prospect is wide.

Description

A kind of carbon coating manganese pyrophosphate sodium@graphene oxides with sandwich structure are combined Material and its preparation method and application
Technical field
The present invention relates to a kind of sodium-ion battery positive material, and in particular to a kind of carbon coating with sandwich structure is burnt Composite positive pole of manganese phosphate sodium and graphene oxide and preparation method thereof, and composite answering as sodium-ion battery With belonging to sodium-ion battery field.
Background technology
Lithium ion battery is due to advantages such as high-energy-density, high stability, long-lives, having occupied rapidly portable Electronic product (notebook computer, intelligent mobile equipment, tablet personal computer etc.) market, and constantly oozed to electric vehicle field Enter.But, lithium resource reserves in the earth's crust are low, and Regional Distribution is uneven so that lithium ion battery is in a wide range of popularization and application During lithium valency constantly rise, cause lithium ion battery to hold at high price.Therefore, lithium ion battery is led in extensive storing up electricity The application in domain is restricted.Sodium-ion battery is abundant, environment-friendly due to sodium resource reserves, it is considered to be a kind of preferably big Scale storing up electricity application technology and the extensive concern for obtaining the world.
In past tens year, researcher has been carried out widely studied to the positive electrode of sodium-ion battery. In existing positive electrode system, polyanionic chemical combination objects system is considered as the electric positive electrode of sodium of most commercial promise System.In polyanionic chemical combination objects system, pyrophosphate system material is due to open three-dimensional channel and higher The advantage such as structural stability, heat endurance and obtain the attention of researcher.Report that more ferric sodium pyrophosphate has pole at present Good chemical property, reversible specific capacity is close to theoretical specific capacity 95mAh/g under 0.1C multiplying power.But Fe2+/Fe3+Oxygen Change reduction potential relatively low so that ferric sodium pyrophosphate discharge platform is relatively low, therefore energy density is not high.Manganese pyrophosphate sodium has 97.5mAh/g theoretical specific capacity, and 3.7V (vs Na/Na+) more than high voltage, with more preferable storage sodium performance and into This is cheap.However, because manganese pyrophosphate sodium material electric conductivity itself is poor, its as electrode material high rate performance and cyclicity Can be barely satisfactory.In addition, manganese pyrophosphate sodium material synthesis method is generally conventional solid sintering process at present, products therefrom particle diameter is big, Material kinetics poor performance, is unfavorable for the performance of material capacity.Therefore high rate performance, the cyclicity of manganese pyrophosphate sodium how to be improved Material specific capacity, the key issue studied into manganese pyrophosphate sodium as sodium-ion battery positive material and can be lifted.
The content of the invention
The deficiency existed for existing pyrophosphate system sodium ion positive electrode, it is an object of the present invention to carry Supply a kind of stability good, active material good dispersion, pattern is uniform, the carbon coating pyrophosphoric acid with special " sandwich " structure Manganese sodium@graphene oxide composite materials.
Another object of the present invention be to provide it is a kind of it is reproducible, be simple to operate and friendly to environment, it is with low cost, The method of preparation carbon coating manganese pyrophosphate sodium@graphene oxide composite materials with prospects for commercial application.
Third object of the present invention is to be that providing a kind of carbon coating manganese pyrophosphate sodium@graphene oxide composite materials makees For the application of sodium-ion battery positive material, there is high charge-discharge specific capacity, good high rate performance in the sodium-ion battery of preparation And stable circulation performance.
In order to realize above-mentioned technical purpose, the invention provides a kind of carbon coating manganese pyrophosphate with sandwich structure Sodium@graphene oxide composite materials, it is evenly distributed with the graphene oxide sheet heap of carbon coating manganese pyrophosphate sodium particle by surface It is folded to constitute.
Manganese pyrophosphate sodium particle is uniformly coated by carbon-coating in technical scheme, not only increases manganese pyrophosphate sodium The electric conductivity of grain, can obtain higher capacity and play and high rate performance, and carbon-coating clad improves manganese pyrophosphate sodium Heat endurance and chemical stability, are conducive to improving its cycle performance.Meanwhile, carbon coating manganese pyrophosphate sodium particle uniform load exists The surface of graphene oxide sheet, improves the dispersed of carbon coating manganese pyrophosphate sodium particle, obtains higher ratio surface, improves Electro-chemical activity, and graphene oxide sheet constitutes sandwich structure in stacked form with graphene oxide sheet, further increases The stability of composite.
It is preferred that scheme, the carbon coating manganese pyrophosphate sodium@graphene oxide composite materials with sandwich structure Specific surface area is 60~120m2g-1；The particle diameter of carbon coating manganese pyrophosphate sodium particle is 300~1000nm；Preferably 300~ 700nm；More preferably 300~500nm.
More preferably scheme, the quality of the manganese pyrophosphate sodium is the carbon coating manganese pyrophosphate sodium@with sandwich structure The 85%~99% of graphene oxide composite material quality；More preferably 94%~97%；Most preferably 95%~96%.
Present invention also offers a kind of carbon coating manganese pyrophosphate sodium@graphene oxide composite materials with sandwich structure Preparation method, the preparation method is to add graphene oxide in the aqueous solution dissolved with phosphorus source, sodium source, manganese source and complexing agent Afterwards, ultrasonically treated, liquid nitrogen frozen and freeze-drying are carried out successively, obtain presoma；The presoma is placed under protective atmosphere, in 500~800 DEG C are heat-treated, and are produced.
Technical scheme employs complexing agent, and complexing agent one side energy ligand complex metal ion can not only promote Enter the generation of manganese pyrophosphate sodium crystal and dispersed, be conducive to the generation of the uniform manganese pyrophosphate sodium particle of pattern, the opposing party Face, complexing agent is adsorbed in manganese pyrophosphate sodium particle surface as carbon source, complexing agent, by high temperature cabonization, is changed into conductive carbon Clad, can effectively improve the electric conductivity of manganese pyrophosphate sodium material, and improve its stability.In technical scheme Graphene oxide is introduced, using graphene oxide, on the one hand as dispersible carrier, disperses carbon coating manganese pyrophosphate sodium particle Uniformly, and formed interlayer structure, improve the specific surface area and stability of composite, another aspect graphene oxide is compound Material provides good conductive substrates, effectively improves the electrical conductivity of manganese pyrophosphate sodium.Technical solution of the present invention is additionally used Liquid nitrogen frozen and the technique of freeze-drying, can effectively keep the pattern of composite, it is to avoid reunite serious and cause electrochemistry Can reduction.
It is preferred that scheme, the ratio of phosphorus source, sodium source and manganese source is with P:Na:Mn mol ratio is 1.8~2.2:1.8~ 2.2:0.8~1.2 metering；Most preferred ratio is with P:Na:Mn mol ratio is 2:2:1 metering.
It is preferred that scheme, the mol ratio of manganese is 2~5 in the complexing agent and manganese source:1.More preferably 3~4：1, Most preferably 3：1.
More preferably scheme, phosphorus source includes at least one of diammonium hydrogen phosphate, ammonium dihydrogen phosphate, phosphoric acid.
More preferably scheme, the sodium source is included in sodium carbonate, sodium acid carbonate, sodium acetate, sodium oxalate, sodium citrate at least It is a kind of.The sodium source is preferably natrium carbonicum calcinatum and/or sodium acid carbonate, most preferably natrium carbonicum calcinatum.
More preferably scheme, the manganese source is well known to those skilled in the art water-soluble inorganic manganese compound.It is preferred that Manganese source includes at least one of manganese acetate, manganese nitrate, manganese oxalate.Most preferred manganese source is manganese acetate.
Mn described in technical scheme in the aqueous solution2+Concentration is 0.05~0.3mol/L.Mn2+Concentration is preferred For 0.1~0.2mol/L.
More preferably scheme, the complexing agent is at least one of citric acid, oxalic acid, ascorbic acid, sucrose, glucose. Complexing agent is more preferably citric acid and/or sucrose.
More preferably scheme, the heat treatment temperature is 600~700 DEG C, most preferably 600 DEG C.
More preferably scheme, the heat treatment time is 6~12h.
Protective gas is preferably inert gas in technical scheme, for example argon gas.
In technical scheme, the quality of the graphene oxide sheet of addition is burnt for the carbon coating with sandwich structure The 1%~10% of manganese pyrophosphate sodium quality in manganese phosphate sodium@graphene oxide composite materials.
Present invention also offers answering for the carbon coating manganese pyrophosphate sodium@graphene oxide composite materials with sandwich structure With as the positive electrode application of sodium-ion battery.
The preparation side of the carbon coating manganese pyrophosphate sodium@graphene oxide composite materials with sandwich structure of the present invention Method, comprises the following steps：
Step (1)：Four acetate hydrate manganese, ammonium dihydrogen phosphate, natrium carbonicum calcinatum are stoichiometrically weighed, and by complexing agent With Mn2+Mol ratio be 2~5：1 weighs anhydrous citric acid, is then dissolved in deionized water, is sufficiently stirred for obtaining mixing molten Liquid；The Mn of the mixed solution2+Concentration is 0.05~0.3mol/L；
Step (2)：3%~6% graphene oxide of theoretical product quality is added into solution, it is ultrasonically treated 30min, then 80 degree of water-bath 6h, then liquid nitrogen frozen, is placed in freeze drier, by gained presoma as 600 after freezing 8~10h is sintered in~700 DEG C of tube furnace under inert atmosphere, the carbon coating manganese pyrophosphate with sandwich structure is finally obtained Sodium@graphene oxide composite materials.
Present invention additionally comprises by the carbon coating manganese pyrophosphate sodium@graphene oxide composite positive poles with sandwich structure For preparing the positive pole of sodium-ion battery, and test its chemical property.
For example, described carbon coating manganese pyrophosphate sodium@graphene oxide composite materials are mixed with conductive agent and binding agent Afterwards, by being coated on aluminium foil, sodium-ion battery positive pole is made.Conductive agent, the binding agent used can use art technology Material known to personnel.The method that assembling prepares sodium-ion battery positive material also refers to existing method.
For example, " sandwich " structure carbon coating manganese pyrophosphate sodium graphene oxide composite material produced by the present invention is conductive Carbon black and PVDF binding agents are according to 8:1:1 mass ratio is ground, and NMP is added after being sufficiently mixed and forms uniform pulpous state Thing, is coated on aluminium foil as test electrode, and using metallic sodium as to electrode, its electrolyte is 1M NaClO4/ 100%PC, system Standby sodium half-cell tests its chemical property.
Compared with the prior art, the beneficial effect that technical scheme is brought：
The carbon coating manganese pyrophosphate sodium@graphene oxide composite materials of the present invention have special sandwich structure, aoxidize Graphene film is stacked, the dispersed load carbon coating between graphene oxide sheet surface and two pieces of adjacent graphene oxide sheets Manganese pyrophosphate sodium particle.Graphene can not only improve the dispersiveness of carbon coating manganese pyrophosphate sodium particulate active, improve its ratio Surface area, increases avtive spot, improves electro-chemical activity；Graphene oxide sheet forms sandwich with carbon coating manganese pyrophosphate sodium particle Structure, is conducive to improving the physicochemical stability of composite；And graphene oxide is good as carbon coating manganese pyrophosphate sodium particle Good conducting base, improves its electric conductivity, and the capacity that composite positive pole is greatly improved is played and high rate performance.Manganese pyrophosphate sodium Particle is uniformly coated by carbon-coating, not only increases the electric conductivity of manganese pyrophosphate sodium particle, can obtain higher capacity play and High rate performance, and carbon-coating clad improves the heat endurance and chemical stability of manganese pyrophosphate sodium, and being conducive to improvement, it is followed Ring performance.
The carbon coating manganese pyrophosphate sodium@graphene oxide composite materials of the present invention are closed by solwution method combination high-temperature heat treatment Into.Persursor material is synthesized by solwution method, and complexing agent is employed in solwution method, and complexing agent not only plays its complexing, is made again For carbon source, the generation of manganese pyrophosphate sodium crystal and uniform dispersiveness, in addition at high temperature, itself transformation on the one hand can be promoted For conductive carbon, the electric conductivity of manganese pyrophosphate sodium material can be effectively improved.Graphene oxide is additionally used as carrier simultaneously Material, the polar group that graphene oxide is included using its surface can promote the scattered of manganese pyrophosphate sodium crystal, easily obtain grain Footpath is uniform, the good manganese pyrophosphate sodium crystal of pattern, and graphene oxide provides good conductive substrates for composite, has Effect improves the electrical conductivity of manganese pyrophosphate sodium.Presoma employs liquid nitrogen frozen and freeze-drying effectively keeps material morphology, keeps away Exempt to reunite serious and cause chemical property to reduce.High-temperature heat treatment process, realizes generation and the focusing phosphorus of carbon coating layer The synchronous realization of the in-stiu coating of sour manganese sodium particle, enormously simplify processing step.
The carbon coating manganese pyrophosphate sodium@graphene oxide composite materials with sandwich structure of the present invention have high electrification Activity is learned, high physicochemical stability and high security are used for sodium-ion battery as sodium ion positive electrode, shown excellent Different chemical property, sodium-ion battery is under 0.2C multiplying power, and circulation 50 encloses specific discharge capacity up to 70mAh/g, and capacity is protected Holdup is up to more than 90%.
The method of carbon coating manganese pyrophosphate sodium@graphene oxide composite material of the preparation with sandwich structure of the present invention It is simple and reliable, environment-friendly, " Na-Mn-P-O " system aboundresources, with low cost, industrial applications have a extensive future.
Brief description of the drawings
【Fig. 1】It is compound just for the obtained carbon coating manganese pyrophosphate sodium@graphene oxides with sandwich structure of embodiment 1 The X ray diffracting spectrum (XRD) of pole material；
【Fig. 2】It is compound just for the obtained carbon coating manganese pyrophosphate sodium@graphene oxides with sandwich structure of embodiment 1 The scanning electron microscope (SEM) photograph (SEM) of pole material；
【Fig. 3】The carbon coating manganese pyrophosphate sodium@graphene oxide anode composite materials of the sandwich structure made from embodiment 1 Charging and discharging curve under the 0.1C multiplying powers of the sodium-ion battery of material assembling；
【Fig. 4】The carbon coating manganese pyrophosphate sodium@graphene oxide anode composite materials of tool sandwich structure are made for embodiment 1 Expect that the 0.1mV/s of the sodium-ion battery of assembling sweeps the CV curves under speed.
Embodiment
Following examples are intended to be described in further details present invention；And the protection domain of the claims in the present invention It is not limited by the example.
Embodiment 1
Take first the acetate hydrate manganese of 0.005mol tetra-, 0.01mol ammonium dihydrogen phosphates, 0.005mol natrium carbonicum calcinatums and 2.88g is (with manganese mol ratio 3：1) anhydrous citric acid, is dissolved in 50mL deionized waters, is sufficiently stirred for, obtain settled solution.So Add in the solution after 0.067g (the 5% of manganese pyrophosphate sodium quality) graphene oxide, ultrasonically treated 30min afterwards, 80 DEG C of water-baths 6h.Solution is subjected to liquid nitrogen frozen, is subsequently placed in freeze drier and freezes.By gained presoma as inert atmosphere tube furnace In, 600 DEG C of sintering 9h, resulting solid product is the carbon coating manganese pyrophosphate sodium@graphite oxides with sandwich structure Alkene composite positive pole.The X of obtained " sandwich " structure carbon coating manganese pyrophosphate sodium graphene oxide composite positive pole X ray diffraction collection of illustrative plates (XRD) is shown in Fig. 1.The obtained carbon coating manganese pyrophosphate sodium@graphene oxides with sandwich structure are answered The scanning electron microscope (SEM) photograph (SEM) for closing positive electrode is shown in Fig. 2, as shown in Figure 2, and the material manganese pyrophosphate sodium is combined with graphene uniform, Manganese pyrophosphate sodium grain diameter is 300~500nm, and specific surface area is 110m2 g-1。
Button cell is assembled into using sodium-ion battery composite positive pole manufactured in the present embodiment and sodium piece, from 0.2C Circulation it can be seen from the figure that, circulation 50 encloses specific discharge capacities and reaches 73mAh/g, and capability retention is up to more than 90%.
Embodiment 2
Take first the acetate hydrate manganese of 0.005mol tetra-, 0.01mol ammonium dihydrogen phosphates, 0.005mol natrium carbonicum calcinatums and 3.84g is (with manganese mol ratio 4：1) anhydrous citric acid, is dissolved in 50mL deionized waters, is sufficiently stirred for, obtain settled solution.So Add in the solution after 0.067g (the 5% of manganese pyrophosphate sodium quality) graphene oxide, ultrasonically treated 30min afterwards, 80 DEG C of water-baths 6h, then carries out liquid nitrogen frozen, is subsequently placed in freeze drier and freezes.By gained presoma as inert atmosphere tube furnace In, 600 DEG C of sintering 9h, resulting solid product is the carbon coating manganese pyrophosphate sodium@graphite oxides with sandwich structure Alkene composite positive pole.Manganese pyrophosphate sodium grain diameter is 300~500nm, and specific surface area is 110m2g-1。
Button cell is assembled into using sodium-ion battery composite positive pole manufactured in the present embodiment and sodium piece, in 0.2C Multiplying power under, circulation 50 circle after specific capacity be 65mAh/g.Illustrate excessive electric conductivity and bad machine carbon does not have to material property It is obviously improved effect.
Embodiment 3
Take first the acetate hydrate manganese of 0.005mol tetra-, 0.01mol ammonium dihydrogen phosphates, 0.005mol natrium carbonicum calcinatums and 2.88g is (with manganese mol ratio 3：1) anhydrous citric acid, is dissolved in 50mL deionized waters, is sufficiently stirred for, obtain settled solution.So Add in the solution after 0.134g (the 8% of manganese pyrophosphate sodium quality) graphene oxide, ultrasonically treated 30min afterwards, 80 DEG C of water-baths 6h, carries out liquid nitrogen frozen, is subsequently placed in freeze drier and freezes.By gained presoma as in inert atmosphere tube furnace, 600 DEG C sintering 9h, resulting solid product is that the carbon coating manganese pyrophosphate sodium@graphene oxides with sandwich structure are combined Positive electrode.
Button cell is assembled into 0.2C's using sodium-ion battery composite positive pole manufactured in the present embodiment and sodium piece Under multiplying power, specific capacity is 70mAh/g after the circle of circulation 50.Illustrate that excessive graphene is not obviously improved effect to material property.
Embodiment 4
Take first the acetate hydrate manganese of 0.005mol tetra-, 0.01mol ammonium dihydrogen phosphates, 0.005mol natrium carbonicum calcinatums and 2.88g is (with manganese mol ratio 3：1) anhydrous citric acid, is dissolved in 40mL deionized waters, is sufficiently stirred for, obtain settled solution.So Add in the solution after 0.067g (the 5% of manganese pyrophosphate sodium quality) graphene oxide, ultrasonically treated 30min afterwards, 80 DEG C of water-baths 6h, carries out liquid nitrogen frozen, is subsequently placed in freeze drier and freezes.By gained presoma as in inert atmosphere tube furnace, 600 DEG C sintering 9h, resulting solid product is that the carbon coating manganese pyrophosphate sodium@graphene oxides with sandwich structure are combined Positive electrode.Manganese pyrophosphate sodium grain diameter is 500~800nm, and specific surface area is 80m2g-1。
Button cell is assembled into using sodium-ion battery composite positive pole manufactured in the present embodiment and sodium piece, 0.2C's Under multiplying power, specific capacity is 62mAh/g after the circle of circulation 50.Illustrate that solution solubility influences material particle size.
Embodiment 5
Take first the acetate hydrate manganese of 0.005mol tetra-, 0.01mol ammonium dihydrogen phosphates, 0.005mol natrium carbonicum calcinatums and 2.64g is (with manganese mol ratio 3：1) ascorbic acid, is dissolved in 60mL deionized waters, is sufficiently stirred for, obtain settled solution.Then Add in the solution after 0.067g (the 5% of manganese pyrophosphate sodium quality) graphene oxide, ultrasonically treated 30min, 80 DEG C of water-bath 6h, Liquid nitrogen frozen is carried out, is subsequently placed in freeze drier and freezes.By gained presoma as in inert atmosphere tube furnace, 600 DEG C 12h is sintered, resulting solid product is that the carbon coating manganese pyrophosphate sodium@graphene oxides with sandwich structure are compound just Pole material.
Button cell is assembled into using sodium-ion battery composite positive pole manufactured in the present embodiment and sodium piece, 0.2C's Under multiplying power, specific capacity is 62mAh/g after the circle of circulation 50.Illustrate that the chemical property for sintering 12h materials is decreased obviously.
Embodiment 6
Take first the acetate hydrate manganese of 0.005mol tetra-, 0.01mol ammonium dihydrogen phosphates, 0.005mol natrium carbonicum calcinatums and 2.64g is (with manganese mol ratio 3：1) ascorbic acid, is dissolved in 60mL deionized waters, is sufficiently stirred for, obtain settled solution.Then Add in the solution after 0.067g (the 5% of manganese pyrophosphate sodium quality) graphene oxide, ultrasonically treated 30min, 80 DEG C of water-bath 6h, Liquid nitrogen frozen is carried out, is subsequently placed in freeze drier and freezes.By gained presoma as in inert atmosphere tube furnace, 600 DEG C 6h is sintered, resulting solid product is that the carbon coating manganese pyrophosphate sodium@graphene oxides with sandwich structure are compound just Pole material.
Button cell is assembled into using sodium-ion battery composite positive pole manufactured in the present embodiment and sodium piece, 0.2C's Under multiplying power, specific capacity is 59mAh/g after the circle of circulation 50.Illustrate that the chemical property for sintering 6h materials is decreased obviously.
Embodiment 7
Take first the acetate hydrate manganese of 0.005mol tetra-, 0.01mol ammonium dihydrogen phosphates, 0.005mol natrium carbonicum calcinatums and 2.64g is (with manganese mol ratio 3：1) ascorbic acid, is dissolved in 60mL deionized waters, is sufficiently stirred for, obtain settled solution.Then Add in the solution after 0.067g (the 5% of manganese pyrophosphate sodium quality) graphene oxide, ultrasonically treated 30min, 80 DEG C of water-bath 6h, Liquid nitrogen frozen is carried out, is subsequently placed in freeze drier and freezes.By gained presoma as in inert atmosphere tube furnace, 600 DEG C 8h is sintered, resulting solid product is that the carbon coating manganese pyrophosphate sodium@graphene oxides with sandwich structure are compound just Pole material.
Button cell is assembled into using sodium-ion battery composite positive pole manufactured in the present embodiment and sodium piece, 0.2C's Under multiplying power, specific capacity is 67mAh/g after the circle of circulation 50.Illustrate that the chemical property for sintering 8h materials is preferable.
Embodiment 8
Take first the acetate hydrate manganese of 0.005mol tetra-, 0.01mol ammonium dihydrogen phosphates, 0.005mol natrium carbonicum calcinatums and 2.64g is (with manganese mol ratio 3：1) ascorbic acid, is dissolved in 60mL deionized waters, is sufficiently stirred for, obtain settled solution.Then Add in the solution after 0.067g (the 5% of manganese pyrophosphate sodium quality) graphene oxide, ultrasonically treated 30min, 80 DEG C of water-bath 6h, Liquid nitrogen frozen is carried out, is subsequently placed in freeze drier and freezes.By gained presoma as in inert atmosphere tube furnace, 600 DEG C 10h is sintered, resulting solid product is that the carbon coating manganese pyrophosphate sodium@graphene oxides with sandwich structure are compound just Pole material.
Button cell is assembled into using sodium-ion battery composite positive pole manufactured in the present embodiment and sodium piece, 0.2C's Under multiplying power, specific capacity is 67mAh/g after the circle of circulation 50.Illustrate that the chemical property for sintering 10h materials is preferable.
Embodiment 9
Take first the acetate hydrate manganese of 0.005mol tetra-, 0.01mol ammonium dihydrogen phosphates, 0.005mol natrium carbonicum calcinatums and 2.88g is (with manganese mol ratio 3：1) anhydrous citric acid, is dissolved in 60mL deionized waters, is sufficiently stirred for, obtain settled solution.So Add in the solution after 0.067g (the 5% of manganese pyrophosphate sodium quality) graphene oxide, ultrasonically treated 30min afterwards, 80 DEG C of water-baths 6h, carries out liquid nitrogen frozen, is subsequently placed in freeze drier and freezes.By gained presoma as in inert atmosphere tube furnace, 500 DEG C sintering 9h, resulting solid product is that the carbon coating manganese pyrophosphate sodium@graphene oxides with sandwich structure are combined Positive electrode.
Button cell is assembled into using sodium-ion battery composite positive pole manufactured in the present embodiment and sodium piece, 0.2C's Under multiplying power, specific capacity is 56mAh/g after the circle of circulation 50.Say that the material property of 500 DEG C of sintering is substantially poor.
Embodiment 10
Take first the acetate hydrate manganese of 0.005mol tetra-, 0.01mol ammonium dihydrogen phosphates, 0.005mol natrium carbonicum calcinatums and 2.88g is (with manganese mol ratio 3：1) anhydrous citric acid, is dissolved in 60mL deionized waters, is sufficiently stirred for, obtain settled solution.So Add in the solution after 0.067g (the 5% of manganese pyrophosphate sodium quality) graphene oxide, ultrasonically treated 30min afterwards, 80 DEG C of water-baths 6h, carries out liquid nitrogen frozen, is subsequently placed in freeze drier and freezes.By gained presoma as in inert atmosphere tube furnace, 700 DEG C sintering 9h, resulting solid product is that the carbon coating manganese pyrophosphate sodium@graphene oxides with sandwich structure are combined Positive electrode.
Button cell, 0.2C times are assembled into using sodium-ion battery composite positive pole manufactured in the present embodiment and sodium piece Under rate, specific capacity is 61mAh/g after the circle of circulation 50.
Embodiment 11
Take first the acetate hydrate manganese of 0.005mol tetra-, 0.01mol ammonium dihydrogen phosphates, 0.005mol natrium carbonicum calcinatums and 2.88g is (with manganese mol ratio 3：1) anhydrous citric acid, is dissolved in 60mL deionized waters, is sufficiently stirred for, obtain settled solution.So Add in the solution after 0.412g (the 5% of manganese pyrophosphate sodium quality) graphene oxide, ultrasonically treated 30min afterwards, 80 DEG C of water-baths 6h, carries out liquid nitrogen frozen, is subsequently placed in freeze drier and freezes.By gained presoma as in inert atmosphere tube furnace, 800 DEG C sintering 9h, resulting solid product is the structure carbon coating manganese pyrophosphate sodium graphene oxide with sandwich structure Composite positive pole.
Button cell is assembled into using sodium-ion battery composite positive pole manufactured in the present embodiment and sodium piece, 0.2C's Under multiplying power, specific capacity is 52mAh/g after the circle of circulation 50.
Comparative example 1
The acetate hydrate manganese of 0.005mol tetra-, 0.01mol ammonium dihydrogen phosphates, 0.005mol natrium carbonicum calcinatums and 0g are taken first Anhydrous citric acid, is dissolved in 60mL deionized waters, is sufficiently stirred for, obtain settled solution.Then 0.067g is added in the solution (5%) after graphene oxide, ultrasonically treated 30min, 80 DEG C of water-bath 6h carry out liquid nitrogen frozen, are subsequently placed in freeze drier It is lyophilized.By gained presoma as in inert atmosphere tube furnace, 600 DEG C of sintering 9h collect product.XRD is not detected by pyrophosphoric acid The thing phase of manganese sodium.
Comparative example 2
Take first the acetate hydrate manganese of 0.005mol tetra-, 0.01mol ammonium dihydrogen phosphates, 0.005mol natrium carbonicum calcinatums and 2.88g is (with manganese mol ratio 3：1) anhydrous citric acid, is dissolved in 60mL deionized waters, is sufficiently stirred for, obtain settled solution.80 DEG C water-bath 6h, carries out liquid nitrogen frozen, is subsequently placed in freeze drier and freezes.By gained presoma as inert atmosphere tube furnace In, 600 DEG C of sintering 9h collect product.XRD shows the thing phase of manganese pyrophosphate sodium.Using sodium ion manufactured in the present embodiment electricity Pond composite positive pole is assembled into button cell with sodium piece, and chemical property is substantially reduced.Illustrate that graphene is carried to material property Rise most important.
Comparative example 3
Take first the acetate hydrate manganese of 0.005mol tetra-, 0.01mol ammonium dihydrogen phosphates, 0.005mol natrium carbonicum calcinatums and 1.92g is (with manganese mol ratio 1：1) anhydrous citric acid, is dissolved in 60mL deionized waters, is sufficiently stirred for, obtain settled solution.So Add in the solution after 0.067g (the 5% of manganese pyrophosphate sodium quality) graphene oxide, ultrasonically treated 30min afterwards, 80 DEG C of water-baths 6h, carries out liquid nitrogen frozen, is subsequently placed in freeze drier and freezes.By gained presoma as in inert atmosphere tube furnace, 600 DEG C sintering 9h, collect product.XRD is displayed without the thing phase of manganese pyrophosphate sodium,
Comparative example 4
The acetate hydrate manganese of 0.03mol tetra-, 0.06mol ammonium dihydrogen phosphates, 0.03mol natrium carbonicum calcinatums and 2.88g are taken first (with manganese mol ratio 3：1) anhydrous citric acid, is dissolved in 60mL deionized waters, is sufficiently stirred for, obtain settled solution.Then molten Add after 0.067g (the 5% of manganese pyrophosphate sodium quality) graphene oxide, ultrasonically treated 30min, 80 DEG C of water-bath 6h, carry out in liquid Liquid nitrogen frozen, is subsequently placed in freeze drier and freezes.By gained presoma as in inert atmosphere tube furnace, 400 DEG C sinter 9h, collects product.XRD is not detected by the thing phase of manganese pyrophosphate sodium.
Comparative example 5
Take first the acetate hydrate manganese of 0.005mol tetra-, 0.01mol ammonium dihydrogen phosphates, 0.005mol natrium carbonicum calcinatums and 2.88g is (with manganese mol ratio 3：1) anhydrous citric acid, is dissolved in 60mL deionized waters, is sufficiently stirred for, obtain settled solution.So Add in the solution after 0.067g (the 5% of manganese pyrophosphate sodium quality) graphene oxide, ultrasonically treated 30min afterwards, 80 DEG C of water-baths 6h, carries out liquid nitrogen frozen, is subsequently placed in freeze drier and freezes.By gained presoma as in inert atmosphere tube furnace, 900 DEG C sintering 9h, collect product.XRD is not detected by the thing phase of manganese pyrophosphate sodium.

Claims (9)

1. a kind of carbon coating manganese pyrophosphate sodium@graphene oxide composite materials with sandwich structure, it is characterised in that：By table The graphene oxide sheet that face is evenly distributed with carbon coating manganese pyrophosphate sodium particle stacks composition.
2. the carbon coating manganese pyrophosphate sodium@graphene oxide composite materials according to claim 1 with sandwich structure, It is characterized in that：The specific surface area of the carbon coating manganese pyrophosphate sodium@graphene oxide composite materials with sandwich structure For 60~120m2g-1；The particle diameter of the carbon coating manganese pyrophosphate sodium particle is 300~1000nm.
3. the carbon coating manganese pyrophosphate sodium@graphene oxide composite woods according to claim 1 or 2 with sandwich structure Material, it is characterised in that：The quality of the manganese pyrophosphate sodium is the carbon coating manganese pyrophosphate sodium@graphite oxides with sandwich structure The 85%~99% of alkene composite quality.
4. the carbon coating manganese pyrophosphate sodium@graphene oxides with sandwich structure described in any one of claims 1 to 3 are combined The preparation method of material, it is characterised in that：Graphite oxide is added in the aqueous solution dissolved with phosphorus source, sodium source, manganese source and complexing agent After alkene, ultrasonically treated, liquid nitrogen frozen and freeze-drying are carried out successively, presoma is obtained；The presoma is placed under protective atmosphere, It is heat-treated, is produced in 500~800 DEG C.
5. the carbon coating manganese pyrophosphate sodium@graphene oxide composite materials according to claim 4 with sandwich structure Preparation method, it is characterised in that：
The ratio of phosphorus source, sodium source and manganese source is with P:Na:Mn mol ratio is 1.8~2.2:1.8~2.2:0.8~1.2 metering；Institute The mol ratio for stating complexing agent and manganese in manganese source is 2~5:1.
6. the carbon coating manganese pyrophosphate sodium@graphene oxide composite materials according to claim 5 with sandwich structure Preparation method, it is characterised in that：
Phosphorus source includes at least one of diammonium hydrogen phosphate, ammonium dihydrogen phosphate, phosphoric acid；
The sodium source includes at least one of sodium carbonate, sodium acid carbonate, sodium acetate, sodium oxalate, sodium citrate；
The manganese source includes at least one of manganese acetate, manganese nitrate, manganese oxalate；
The complexing agent includes at least one of citric acid, oxalic acid, ascorbic acid, sucrose, glucose.
7. the carbon coating manganese pyrophosphate sodium@graphene oxides with sandwich structure according to any one of claim 4~6 The preparation method of composite, it is characterised in that：The heat treatment temperature is 600~700 DEG C.
8. the carbon coating manganese pyrophosphate sodium@graphene oxide composite materials according to claim 7 with sandwich structure Preparation method, it is characterised in that：The heat treatment time is 6~12h.
9. the carbon coating manganese pyrophosphate sodium@graphene oxides with sandwich structure described in any one of claims 1 to 3 are combined The application of material, it is characterised in that：It is used as the positive electrode application of sodium-ion battery.
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CN110217771A (en) * 2019-05-21 2019-09-10 中南大学 A kind of manganese pyrophosphate polyanionic lithium cell cathode material and preparation method thereof
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