CN116207267A - Carbon-sulfur coated polyanion sodium ion battery positive electrode material and preparation method thereof - Google Patents

Carbon-sulfur coated polyanion sodium ion battery positive electrode material and preparation method thereof Download PDF

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CN116207267A
CN116207267A CN202310467191.1A CN202310467191A CN116207267A CN 116207267 A CN116207267 A CN 116207267A CN 202310467191 A CN202310467191 A CN 202310467191A CN 116207267 A CN116207267 A CN 116207267A
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sulfur
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张惠兵
赵阿龙
曹余良
范海满
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Shenzhen Jana Energy Technology Co ltd
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Abstract

The invention discloses a carbon-sulfur coated polyanion type sodium ion battery positive electrode material and a preparation method thereof, the polyanion type sodium ion battery positive electrode material comprises polyanion positive electrode material particles, the surfaces of the polyanion positive electrode material particles are provided with a carbon-sulfur coating layer, the thickness of the carbon-sulfur coating layer is 0.1-50 nm, sulfur accounts for 0.1-10% of the total coating layer mass, and the density is 0.1-2.5 g/cm 3 . The carbon-sulfur coated polyanion type sodium ion battery anode material of the inventionThe material and the preparation method thereof have the characteristics of high sodium ion diffusion speed, stable and uniform interface, good electronic conductivity and excellent processability.

Description

Carbon-sulfur coated polyanion sodium ion battery positive electrode material and preparation method thereof
Technical Field
The invention relates to the technical field of sodium ion batteries, in particular to a carbon-sulfur coated polyanion type sodium ion battery anode material and a preparation method thereof.
Background
With the development of new energy industry, the energy storage requirement is particularly vigorous. In view of the important role of secondary batteries in large-scale energy storage, and the stability, use cost and environmental friendliness of secondary batteries are all of great advantages, the secondary batteries become the first choice.
Among the existing secondary batteries, lithium/sodium ion batteries are becoming the main secondary battery type, and particularly, research on lithium ion batteries has been quite mature. However, the lithium resource is unevenly distributed, and the lithium resource cannot meet the requirement of large-scale energy storage due to factors such as insufficient reserves. Correspondingly, the sodium ion battery has a working principle similar to that of a lithium ion battery, has abundant sodium resource reserves, low cost and no pollution to the environment, and is the technology most hopefully applied to large-scale energy storage at present.
The current main current positive electrode materials of sodium ion batteries comprise transition metal oxides, polyanions, prussian blue compounds and organic compounds, and each material has respective advantages and disadvantages. For example, the transition metal oxide is easy to absorb water and react with air, and is often accompanied by various phase changes in the process of sodium ion deintercalation, so that the cycle stability is poor; for example, the transition metal ion of Prussian blue compounds is dissolved, and the crystal water is difficult to remove, and gas is easily generated at a high potential. The electron conductivity of the organic cathode material is generally poor and is easily dissolved in an organic electrolyte.
In contrast, polyanionic materials tend to have an open three-dimensional framework structure, and thus have good cycling stability and excellent rate capability, which is the best choice for commercial sodium ion batteries. However, polyanionic materials generally have low electron conductance and require carbon modification on their surfaces to increase their electron conductivity. Taking lithium iron phosphate as a lithium battery anode material as an example, the realization of surface carbon coating through pyrolysis of glucose is already a very mature process. Generally, a carbon coating of about 1-2% can meet the electrical conductivity requirements of lithium iron phosphate. However, for the sodium electric polyanion type positive electrode material, the primary crystal grain size is small, the specific surface is large, and the carbon coating amount of 1-2% is insufficient to form a uniform and compact coating layer on the surface of the material, so that electrolyte is continuously decomposed on the particle surface during the battery circulation process, and the battery is deteriorated.
In recent years, research on sodium-electric polyanion cathode materials mainly adopts a mode of coating excessive carbon (> 5%) to compensate the problem of uneven and non-compact carbon coating, and further obtains the polyanion cathode materials with stable circulation. For example, in the Chinese patent application CN110226252A polyanionic sodium ion battery anode material and the preparation method thereof, the addition amount of the carbon source is 5-20wt% of the total mass of the solid raw material; in the positive electrode material of the polyanionic sodium ion battery of Chinese patent application No. CN106784727A and the preparation method thereof, the addition amount of the stearic acid of the carbon source in the example 1 is 10.76 weight percent of the total mass of the solid raw material, the addition amount of the citric acid of the carbon source in the example 2 is 5.61 weight percent of the total mass of the solid raw material, and the addition amount of the sucrose of the carbon source in the example 3 is 8.35 weight percent of the total mass of the solid raw material. However, the problem is followed that excessive carbon coating not only reduces the average gram capacity of the material, but also the larger specific surface area causes powder to fall off in the subsequent homogenizing and film coating processes, thus seriously deteriorating the processing performance.
Disclosure of Invention
The invention aims to provide a carbon-sulfur coated polyanion type sodium ion battery anode material and a preparation method thereof, and the carbon-sulfur coated polyanion type sodium ion battery anode material has the characteristics of high sodium ion diffusion speed, stable and uniform interface, good electronic conductivity and excellent processability.
The invention can be realized by the following technical scheme:
the invention discloses a carbon-sulfur coated polyanion sodium ion battery positive electrode material, which comprises polyanion positive electrode material particles, wherein the surfaces of the polyanion positive electrode material particles are coated with a carbon-sulfur coating layer, the thickness of the carbon-sulfur coating layer is 0.1-50 nm, sulfur accounts for 0.1-10% of the total coating layer mass, and the density is 0.1-2.5 g/cm 3 。
According to the invention, the sulfur element is introduced into the carbon coating layer to form the sulfur-carbon composite coating layer, so that the uniform and compact coating can be formed on the surface of the material under the condition of lower carbon coating amount (2%) due to stronger binding force between sulfur and carbon, thereby avoiding the decomposition of electrolyte at the interface of the material and improving the electronic conductivity and the cycling stability of the material.
Further, the general formula of the polyanionic positive electrode material is Na a M b (XO 4 ) c Y d Wherein M is one or more than two of Fe, mn, V, cr, ti, ni and/or Co; x is Si and/or P; y is F, P 2 O 7 4- One or two or more of them; a has a value of 0<a<5.0；0<b<4.0；0<c<4.0；0<d<4.0。
Further, the polyanion positive electrode material is NaFePO 4 、NaMnPO 4 、NaNiPO 4 、NaCoPO 4 、Na 2 FeSiO 4 、Na 2 MnSiO 4 、Na 2 CoSiO 4 、Na 2 NiSiO 4 、Na 2 FeP 2 O 7 、Na 2 MnP 2 O 7 、Na 2 CoP 2 O 7 、Na 2 NiP 2 O 7 、Na 4 Fe 3 (PO 4 ) 2 P 2 O 7 、Na 4 Mn 3 (PO 4 ) 2 P 2 O 7 、Na 4 Co 3 (PO 4 ) 2 P 2 O 7 、Na 4 Ni 3 (PO 4 ) 2 P 2 O 7 、Na 3 V 2 (PO 4 ) 3 、Na 4 VMn(PO 4 ) 3 、Na 4 VFe(PO 4 ) 3 、Na 4 MnCr(PO 4 ) 3 、Na 3 MnTi(PO 4 ) 3 、Na 3 VCr(PO 4 ) 3 、Na 3 V 2 (PO 4 ) 2 F 3 、NaFePO 4 F、NaMnPO 4 F、NaCoPO 4 F、NaNiPO 4 F and/or Na 3 (VO x PO 4 ) 2 F 3-2x One or two or more of them.
The invention also provides a preparation method for protecting the carbon-sulfur coated polyanion sodium ion battery anode material, which comprises the following steps:
s1, mixing: the sodium source, the transition metal source and the anion source are mixed according to the stoichiometric ratio Na in the molecular formula a M b (XO 4 ) c Y d Weighing raw materials and uniformly mixing to obtain a primary mixed material;
s2, drying: drying the primary mixed material in the step S1 to obtain dried precursor powder;
s3, coating: mixing and ball milling the precursor powder in the step S2 with a carbon source and a sulfur source to realize coating of a powder interface to obtain coated powder;
s4, sintering: and (3) sintering the coated powder in the step (S3) at high temperature to obtain the carbon-sulfur coated modified polyanion sodium ion battery anode material.
Further, the sodium source is one or more of sodium chloride, sodium sulfate, sodium carbonate, sodium hydroxide, sodium oxalate, sodium citrate, sodium gluconate, sodium dodecyl benzene sulfonate, sodium ethoxide and/or sodium acetylene.
Further, the transition metal source is a Fe source, a Mn source, a V source, a Cr source, a Ti source, a Ni source and/or a Co source; the Fe source is one or more than two of iron powder, iron oxide, ferric nitrate, ferric sulfate, ferric chloride, ferric citrate, ferric acetate and/or ferric succinate; mn source is one or more than two of manganese salts such as manganese oxide, manganese nitrate, manganese acetate, manganese chloride, manganese sulfate and the like; the V source is vanadium oxide and/or ammonium metavanadate; the Cr source is one or more than two of chromium oxide, sodium chromate and/or chromium hydroxide; the Ti source is one or more than two of titanium oxide, titanium sulfate and/or titanium sulfate acyl; the Ni source is one or more than two of nickel oxide, nickel hydroxide and/or nickel sulfate; the Co source is one or more of cobalt oxide, cobalt sulfate and/or cobalt chloride.
Further, the anion source is Si source, P source, F source and/or P source 2 O 7 4- A source; the Si source is silicic acid, sodium silicate and/or siliconOne or more than two of ethyl acetate; the P source is one or more than two of phosphoric acid, sodium phosphate, sodium hydrogen phosphate, sodium dihydrogen phosphate and/or ammonium dihydrogen phosphate; the F source is one or more than two of sodium fluoride, ammonium fluoride and/or hydrofluoric acid.
Further, the addition amount of the carbon source is 0.5-5wt% of the total mass of the solid raw material, the addition amount of the sulfur source is 0.5-2wt% of the total mass of the solid raw material, and the total addition amount of the carbon source and the sulfur source is within 5wt% of the total mass of the solid raw material;
further, the carbon source is one or more than two of citric acid, glucose, sucrose, starch, maltose, lactose, cyclodextrin, polyethylene glycol, polyvinyl alcohol, carbon powder, carbon nano tube and/or graphene.
Further, the sulfur source is a mercaptan compound, a thiophenol compound and/or a thioether compound, the mercaptan compound is one or more than two of methyl mercaptan, ethyl dithiol, 1-propylmercaptan and/or 1-3 propyldithiol, and the thiophenol compound is one or more than two of o-thiophenol, p-methylthiophenol and/or thiophenol; the thioether compound is one or more of diallyl sulfide, dibutyl sulfide and/or dimethyl sulfide.
In step S1, the mixing mode is liquid phase mixing, semi-solid phase mixing and/or solid phase mixing.
Further, in step S2, the drying mode is vacuum drying, low temperature drying, spray drying and/or high temperature drying.
Further, in the step S3, a ball milling mode is adopted for mixing the precursor powder, the carbon source and the sulfur source, and the weight ratio of the ball materials is 5-20: 1, the rotating speed is 1-50 Hz, and the time length is more than 0.5H.
Further, in step S4, the sintering temperature is 500-800 ℃, and the temperature rising rate is 0.1-10 DEG Cmin -1 The heat preservation time is longer than 1H.
Further, in step S1, the mixing process is assisted by ultrasonic dispersion, mechanical stirring, ball milling and/or sanding; wherein the liquid phase is mixed into a pure solution, and the solid content is 5-40%. The particle size range of solid particles in semi-solid phase mixing and solid phase mixing is 10-300 nm, and the viscosity of the material is 50-400 Pa.S.
Further, in step S2, wherein the vacuum degree of vacuum drying is lower than 0Mpa; the low-temperature drying temperature is lower than 0 ℃; spraying dysphoria air outlet temperature is more than 60 ℃; the high temperature drying temperature is greater than 80 ℃.
The carbon-sulfur coated polyanion type sodium ion battery anode material and the preparation method thereof have the following beneficial effects:
first, the diffusion rate of sodium ions is high, the S-O bonding energy is larger than the C-O bonding energy, and the existence of S-O bonds on the crystal surface can limit the overgrowth of crystal grains of the positive electrode active material in the crystal grain growth process, so that a smaller crystal material is obtained. The smaller grain size shortens the diffusion distance of sodium ions in the material, improves the diffusion speed of the sodium ions, and further improves the rate capability of the battery;
secondly, the interface is stable and uniform, weak interaction between S-C bonds is stronger than that between C-C bonds, and in the sintering process, the existence of S can increase the stacking density of the S-C coating layer, so that the density and uniformity of the S-C coating layer are improved. The S-C coating layer with compact surface avoids direct contact between the electrolyte and the crystal, and reduces the decomposition of the electrolyte and the influence of the electrolyte decomposition products on the crystal;
thirdly, the electron conductivity is good, the doping of S between C layers increases the delocalization of electron cloud outside the C atom nucleus, increases the electron conductivity between materials, further reduces the material impedance, improves the charge-discharge response rate of the battery, and also effectively improves the rate capability of the battery;
fourth, the processability is excellent, compared with the C-C coating, the S-C coating is thinner under the condition of achieving the same densification effect and electron conductivity, the mass ratio of the S-C coating in the material is lower, the requirement can be met only by 1-2wt%, the specific surface is lower, and the subsequent processing treatment of the material is facilitated.
Drawings
FIG. 1 is the Na of example 1 2 FeP 2 O 7 A first-week charge-discharge curve of the S-C electrode;
FIG. 2 is a view of Na in example 1 2 FeP 2 O 7 a/S-C electrode cycle performance curve;
drawings3 is Na in example 1 2 FeP 2 O 7 a/S-C electrode rate discharge curve;
FIG. 4 is Na in comparative example 1 2 FeP 2 O 7 A charge-discharge curve of the first cycle of the electrode;
FIG. 5 is a view of Na in comparative example 1 2 FeP 2 O 7 a/C electrode cycle performance curve;
FIG. 6 is Na in comparative example 1 2 FeP 2 O 7 and/C electrode rate discharge curve.
Detailed Description
In order to make the technical solution of the present invention better understood by those skilled in the art, the following further details of the present invention will be described with reference to examples and drawings.
The invention discloses a carbon-sulfur coated polyanion sodium ion battery positive electrode material, which comprises polyanion positive electrode material particles, wherein the surfaces of the polyanion positive electrode material particles are coated with a carbon-sulfur coating layer, the thickness of the carbon-sulfur coating layer is 0.1-50 nm, sulfur accounts for 0.1-10% of the total coating layer mass, and the density is 0.1-2.5 g/cm 3 。
Further, the general formula of the polyanionic positive electrode material is Na a M b (XO 4 ) c Y d Wherein M is one or more than two of Fe, mn, V, cr, ti, ni and/or Co; x is Si and/or P; y is F, P 2 O 7 4- One or two or more of them; a has a value of 0<a<5.0；0<b<4.0；0<c<4.0；0<d<4.0。
Further, the polyanion positive electrode material is NaFePO 4 、NaMnPO 4 、NaNiPO 4 、NaCoPO 4 、Na 2 FeSiO 4 、Na 2 MnSiO 4 、Na 2 CoSiO 4 、Na 2 NiSiO 4 、Na 2 FeP 2 O 7 、Na 2 MnP 2 O 7 、Na 2 CoP 2 O 7 、Na 2 NiP 2 O 7 、Na 4 Fe 3 (PO 4 ) 2 P 2 O 7 、Na 4 Mn 3 (PO 4 ) 2 P 2 O 7 、Na 4 Co 3 (PO 4 ) 2 P 2 O 7 、Na 4 Ni 3 (PO 4 ) 2 P 2 O 7 、Na 3 V 2 (PO 4 ) 3 、Na 4 VMn(PO 4 ) 3 、Na 4 VFe(PO 4 ) 3 、Na 4 MnCr(PO 4 ) 3 、Na 3 MnTi(PO 4 ) 3 、Na 3 VCr(PO 4 ) 3 、Na 3 V 2 (PO 4 ) 2 F 3 、NaFePO 4 F、NaMnPO 4 F、NaCoPO 4 F、NaNiPO 4 F and/or Na 3 (VO x PO 4 ) 2 F 3-2x One or two or more of them.
The invention also provides a preparation method for protecting the carbon-sulfur coated polyanion sodium ion battery anode material, which comprises the following steps:
s1, mixing: the sodium source, the transition metal source and the anion source are mixed according to the stoichiometric ratio Na in the molecular formula a M b (XO 4 ) c Y d Weighing raw materials and uniformly mixing to obtain a primary mixed material;
s2, drying: drying the primary mixed material in the step S1 to obtain dried precursor powder;
s3, coating: mixing and ball milling the precursor powder in the step S2 with a carbon source and a sulfur source to realize coating of a powder interface to obtain coated powder;
s4, sintering: and (3) sintering the coated powder in the step (S3) at high temperature to obtain the carbon-sulfur coated modified polyanion sodium ion battery anode material.
Further, the sodium source is one or more of sodium chloride, sodium sulfate, sodium carbonate, sodium hydroxide, sodium oxalate, sodium citrate, sodium gluconate, sodium dodecyl benzene sulfonate, sodium ethoxide and/or sodium acetylene.
Further, the transition metal source is a Fe source, a Mn source, a V source, a Cr source, a Ti source, a Ni source and/or a Co source; the Fe source is one or more than two of iron powder, iron oxide, ferric nitrate, ferric sulfate, ferric chloride, ferric citrate, ferric acetate and/or ferric succinate; mn source is one or more than two of manganese salts such as manganese oxide, manganese nitrate, manganese acetate, manganese chloride, manganese sulfate and the like; the V source is vanadium oxide and/or ammonium metavanadate; the Cr source is one or more than two of chromium oxide, sodium chromate and/or chromium hydroxide; the Ti source is one or more than two of titanium oxide, titanium sulfate and/or titanium sulfate acyl; the Ni source is one or more than two of nickel oxide, nickel hydroxide and/or nickel sulfate; the Co source is one or more of cobalt oxide, cobalt sulfate and/or cobalt chloride.
Further, the anion source is Si source, P source, F source and/or P source 2 O 7 4- A source; the Si source is one or more than two of silicic acid, sodium silicate and/or ethyl silicate; the P source is one or more than two of phosphoric acid, sodium phosphate, sodium hydrogen phosphate, sodium dihydrogen phosphate and/or ammonium dihydrogen phosphate; the F source is one or more than two of sodium fluoride, ammonium fluoride and/or hydrofluoric acid.
Further, the addition amount of the carbon source is 0.5-5wt% of the total mass of the solid raw material, the addition amount of the sulfur source is 0.5-2wt% of the total mass of the solid raw material, and the total addition amount of the carbon source and the sulfur source is within 5wt% of the total mass of the solid raw material;
further, the carbon source is one or more than two of citric acid, glucose, sucrose, starch, maltose, lactose, cyclodextrin, polyethylene glycol, polyvinyl alcohol, carbon powder, carbon nano tube and/or graphene.
Further, the sulfur source is a mercaptan compound, a thiophenol compound and/or a thioether compound, the mercaptan compound is one or more than two of methyl mercaptan, ethyl dithiol, 1-propylmercaptan and/or 1-3 propyldithiol, and the thiophenol compound is one or more than two of o-thiophenol, p-methylthiophenol and/or thiophenol; the thioether compound is one or more of diallyl sulfide, dibutyl sulfide and/or dimethyl sulfide.
In step S1, the mixing mode is liquid phase mixing, semi-solid phase mixing and/or solid phase mixing.
Further, in step S2, the drying mode is vacuum drying, low temperature drying, spray drying and/or high temperature drying.
Further, in the step S3, a ball milling mode is adopted for mixing the precursor powder, the carbon source and the sulfur source, and the weight ratio of the ball materials is 5-20: 1, the rotating speed is 1-50 Hz, and the time length is more than 0.5H.
Further, in step S4, the sintering temperature is 500-800 ℃, and the temperature rising rate is 0.1-10 DEG Cmin -1 The heat preservation time is longer than 1H.
Further, in step S1, the mixing process is assisted by ultrasonic dispersion, mechanical stirring, ball milling and/or sanding; wherein the liquid phase is mixed into a pure solution, and the solid content is 5-40%. The particle size range of solid particles in semi-solid phase mixing and solid phase mixing is 10-300 nm, and the viscosity of the material is 50-400 Pa.S.
Further, in step S2, wherein the vacuum degree of vacuum drying is lower than 0Mpa; the low-temperature drying temperature is lower than 0 ℃; spraying dysphoria air outlet temperature is more than 60 ℃; the high temperature drying temperature is greater than 80 ℃.
As the polyanion cathode material has more types, na is respectively selected for effectively explaining the technical effect of the invention 2 FeP 2 O 7 、Na 4 Fe 3 (PO 4 ) 2 P 2 O 7 、Na 3 V 2 (PO 4 ) 3 Comparison was performed. However, this example is not intended to limit the type of materials used for the polyanionic positive electrode material, and the sodium-ion battery positive electrode material or the positive electrode material meeting the general formula requirements listed above also have similar properties and are also within the scope of the present invention.
Example 1
The carbon-sulfur coated polyanion sodium ion battery anode material of the embodiment is specifically Na 2 FeP 2 O 7 The preparation process of the catalyst comprises the following steps:
s1: mixing: dissolving 0.2mol of sodium acetate, 0.1mol of ferric nitrate, 0.2mol of ammonium dihydrogen phosphate and 500mL of deionized water under ultrasonic conditions, and uniformly mixing.
S2: and (3) drying: and (3) spray-drying the precursor solution in the step (S1), and controlling the temperature of air outlet at 100 ℃ to obtain dried precursor powder.
S3: coating: mixing and ball milling the precursor powder dried in the step S2 with glucose and methyl mercaptan, wherein the ball-to-material ratio is 15:1, ball milling frequency 40Hz and duration 5H.
S4: sintering: sintering the powder after ball milling in the step S3, wherein the heating rate is 1 DEG Cmin -1 Preserving heat at 350deg.C for 3H and 550 deg.C for 10H, and naturally cooling to obtain Na 2 FeP 2 O 7 S-C material.
In this example, the carbon source was added in an amount of 2wt% based on the total mass of the solid raw material, and the sulfur source was added in an amount of 1% based on the total mass of the solid raw material.
To polyanion Na 2 FeP 2 O 7 After mixing the S-C material, the acetylene black and the PVDF into homogenate according to the mass ratio of 8:1:1, a 120um four-side preparation machine is used for coating black sizing on aluminum foil, and then the film is dried in a vacuum drying oven at 100 ℃ for 10 hours. The electrode film was punched into a disk having a radius of 0.6mm using a punching machine, and the active material loading was about 2.0mg/cm 2 Sodium metal is used as a counter electrode, and 1mol/L NaClO is used as the counter electrode 4 Ec+dec (1:1vol%) +5% fec was used as an electrolyte, glass fiber was used as a separator, and CR2016 type coin cell was assembled in a glove box. FIG. 1 is Na 2 FeP 2 O 7 And the current density of the first-week charge-discharge curve of the S-C electrode is 0.1C (1C=100 mAh/g), and the reversible discharge specific capacity of the S-C electrode is 98.3mAh/g. FIG. 2 is Na 2 FeP 2 O 7 The capacity retention rate of the S-C electrode is up to 98.2% after 100 weeks of circulation at a 1C rate, and the excellent circulation stability is shown. FIG. 3 is Na 2 FeP 2 O 7 The rate capability of the/S-C electrode, even at a higher rate of 10C, the electrode still had a reversible capacity of 85.1mAh/g, corresponding to a capacity utilization of 86.6%.
Example 2
The carbon-sulfur coated polyanion sodium ion battery anode material of the embodiment is specifically Na 4 Fe 3 (PO 4 ) 2 P 2 O 7 The preparation process of the S-C comprises the following steps:
s1: mixing: 0.3mol of ferrous oxalate, 0.4mol of sodium dihydrogen phosphate and 200mL of deionized water were mixed and milled using a high-energy ball mill. Wherein the ball-to-material ratio, 20:1, the rotating speed is 40Hz, the time is 10H, the solid content is 20%, the particle size range is about 200nm, and the material viscosity is 200Pa.S.
S2: and (3) drying: and (3) heating and drying the precursor solution in the step S1, wherein the heating temperature is controlled at 80 ℃ to obtain dried precursor powder.
S3: coating: mixing and ball milling the precursor powder dried in the step S2 with sucrose and o-phthaldithiol, wherein the ball-to-material ratio is 15:1, ball milling frequency 40Hz and duration 5H.
S4: sintering: sintering the powder after ball milling in the step S3, wherein the heating rate is 1 DEG Cmin -1 Preserving heat at 300 deg.C for 3H and 600 deg.C for 10H, and naturally cooling to obtain Na 4 Fe 3 (PO 4 ) 2 P 2 O 7 S-C material.
In this example, the carbon source was added in an amount of 2wt% based on the total mass of the solid raw material, and the sulfur source was added in an amount of 0.5% based on the total mass of the solid raw material.
To polyanion Na 4 Fe 3 (PO 4 ) 2 P 2 O 7 After mixing the S-C material, the acetylene black and the PVDF into homogenate according to the mass ratio of 8:1:1, a 120um four-side preparation machine is used for coating black sizing on aluminum foil, and then the film is dried in a vacuum drying oven at 100 ℃ for 10 hours. The electrode film was punched into a disk having a radius of 0.6mm using a punching machine, and the active material loading was about 2.0mg/cm 2 Sodium metal is used as a counter electrode, and 1mol/L NaClO is used as the counter electrode 4 Ec+dec (1:1vol%) +5% fec was used as an electrolyte, glass fiber was used as a separator, and CR2016 type coin cell was assembled in a glove box. Na (Na) 4 Fe 3 (PO 4 ) 2 P 2 O 7 And the current density of the first-week charge-discharge curve of the S-C electrode is 0.1C (1C=129 mAh/g), and the reversible discharge specific capacity of the S-C electrode is 110.2mAh/g. Na (Na) 4 Fe 3 (PO 4 ) 2 P 2 O 7 The capacity retention rate of the/S-C electrode was 98.7% after 100 weeks of cycling at a 1C rate, exhibiting excellent cycling stability. Na (Na) 4 Fe 3 (PO 4 ) 2 P 2 O 7 At a higher rate of 10C, the electrode still has a capacity of 90.6mAh/g, corresponding to a capacity utilization of 82.2%. The detailed data pair is shown in table 1.
Example 3
The carbon-sulfur coated polyanion sodium ion battery anode material of the embodiment is specifically Na 3 V 2 (PO 4 ) 3 The preparation process of the S-C comprises the following steps:
s1: mixing: 0.1mol of vanadium pentoxide, 0.3mol of sodium dihydrogen phosphate and 100mL of deionized water were mixed and ground by using a high-energy ball mill. Wherein the ball-to-material ratio, 20:1, the rotating speed is 40Hz, the time is 5H, the solid content is 15%, the particle size range is about 250nm, and the material viscosity is 100Pa.S.
S2: and (3) drying: and (3) vacuum drying the precursor solution in the step S1, wherein the vacuum degree is-0.1 MPa, and obtaining dried precursor powder.
S3: coating: mixing and ball milling the precursor powder dried in the step S2 with citric acid and diallyl sulfide, wherein the ball-to-material ratio is 10:1, ball milling frequency is 30Hz and duration is 10H.
S4: sintering: sintering the powder after ball milling in the step S3, wherein the heating rate is 1 DEG Cmin -1 Preserving heat at 400 deg.C for 3H and 700 deg.C for 12H, and naturally cooling to obtain Na 3 V 2 (PO 4 ) 3 S-C material.
In this example, the carbon source was added in an amount of 3wt% based on the total mass of the solid raw material, and the sulfur source was added in an amount of 1% based on the total mass of the solid raw material.
To polyanion Na 3 V 2 (PO 4 ) 3 After mixing the S-C material, the acetylene black and the PVDF into homogenate according to the mass ratio of 8:1:1, a 120um four-side preparation machine is used for coating black sizing on aluminum foil, and then the film is dried in a vacuum drying oven at 100 ℃ for 10 hours. The electrode film was punched into a disk having a radius of 0.6mm using a punching machine, and the active material loading was about 2.0mg/cm 2 Sodium metal is used as a counter electrode, and 1mol/L NaClO is used as the counter electrode 4 Ec+dec (1:1vol%) +5% fec was used as an electrolyte, glass fiber was used as a separator, and CR2016 type coin cell was assembled in a glove box. Na (Na) 3 V 2 (PO 4 ) 3 And the current density of the first-week charge-discharge curve of the S-C electrode is 0.1C (1C=120 mAh/g), and the reversible discharge specific capacity of the S-C electrode is 115.3mAh/g. Na (Na) 3 V 2 (PO 4 ) 3 The capacity retention rate of the/S-C electrode was 97.9% after 100 weeks of cycling at a 1C rate, exhibiting excellent cycling stability. Na (Na) 3 V 2 (PO 4 ) 3 At a higher rate of 10C, the electrode still has a reversible capacity of 100.2mAh/g, corresponding to a capacity utilization of 86.9%. The detailed data pair is shown in table 1.
Comparative example 1
This comparative example relates to carbon-coated modified polyanionic sodium ion battery cathode material Na 2 FeP 2 O 7 and/C, the preparation process comprises the following steps:
s1: mixing: dissolving 0.2mol of sodium acetate, 0.1mol of ferric nitrate, 0.2mol of ammonium dihydrogen phosphate and 500mL of deionized water under ultrasonic conditions, and uniformly mixing.
S2: and (3) drying: and (3) spray-drying the precursor solution in the step (S1), and controlling the temperature of air outlet at 100 ℃ to obtain dried precursor powder.
S3: coating: mixing and ball milling the precursor powder dried in the step S2 with glucose, wherein the ball-to-material ratio is 15:1, ball milling frequency 40Hz and duration 5H.
S4: sintering: sintering the powder after ball milling in the step S3, wherein the heating rate is 1 DEG Cmin -1 Preserving heat at 350deg.C for 3H and 550 deg.C for 10H, and naturally cooling to obtain Na 2 FeP 2 O 7 and/C material.
To polyanion Na 2 FeP 2 O 7 After mixing the material/C, acetylene black and PVDF into homogenates according to the mass ratio of 8:1:1, a 120um four-side preparation machine was used to coat the black paste on the aluminum foil, and the film was dried in a vacuum drying oven at 100 ℃ for 10 hours. The electrode film was punched into a disk having a radius of 0.6mm using a punching machine, and the active material loading was about 2.0mg/cm 2 Sodium metal is used as a counter electrode, and 1mol/L NaClO is used as the counter electrode 4 Ec+dec (1:1vol%) +5% fec was used as an electrolyte, glass fiber was used as a separator, and CR2016 type coin cell was assembled in a glove box. FIG. 4 is Na 2 FeP 2 O 7 The current density of the charge-discharge curve of the first cycle of the C electrode is 0.1C (1C=100 mAh/g), and the reversible specific discharge capacity of the charge-discharge curve is 90.1mAh/g. FIG. 5 is Na 2 FeP 2 O 7 The capacity retention of the/C electrode was only 73.5% after 100 weeks of cycling at 1C rate, which was far lower than the cycling stability of the S-modified material in application example 1. FIG. 6 is Na 2 FeP 2 O 7 The rate capability of the/C electrode is only 56.3mAh/g, and the capacity utilization rate is 62.5% at a higher rate of 10C, which is far lower than that of the S-modified material.
Comparative example 2
This comparative example relates to carbon-coated modified polyanionic sodium ion battery cathode material Na 4 Fe 3 (PO 4 ) 2 P 2 O 7 and/C, the preparation process comprises the following steps:
s1: mixing: 0.3mol of ferrous oxalate, 0.4mol of sodium dihydrogen phosphate and 200mL of deionized water were mixed and milled using a high-energy ball mill. Wherein the ball-to-material ratio, 20:1, the rotating speed is 40Hz, the time is 10H, the solid content is 20%, the particle size range is about 200nm, and the material viscosity is 200Pa.S.
S2: and (3) drying: and (3) heating and drying the precursor solution in the step S1, wherein the heating temperature is controlled at 80 ℃ to obtain dried precursor powder.
S3: coating: mixing and ball milling the precursor powder dried in the step S2 with sucrose, wherein the ball-to-material ratio is 15:1, ball milling frequency 40Hz and duration 5H.
S4: sintering: sintering the powder after ball milling in the step S3, wherein the heating rate is 1 DEG Cmin -1 Preserving heat at 300 deg.C for 3H and 600 deg.C for 10H, and naturally cooling to obtain Na 4 Fe 3 (PO 4 ) 2 P 2 O 7 and/C material.
To polyanion Na 4 Fe 3 (PO 4 ) 2 P 2 O 7 After mixing the material/C, acetylene black and PVDF into homogenates according to the mass ratio of 8:1:1, a 120um four-side preparation machine was used to coat the black paste on the aluminum foil, and the film was dried in a vacuum drying oven at 100 ℃ for 10 hours. Using a sheet punching machine to punch the electrode film into a circular sheet with the radius of 0.6mm, and carrying active substancesIn an amount of about 2.0mg/cm 2 Sodium metal is used as a counter electrode, and 1mol/L NaClO is used as the counter electrode 4 Ec+dec (1:1vol%) +5% fec was used as an electrolyte, glass fiber was used as a separator, and CR2016 type coin cell was assembled in a glove box. Na (Na) 4 Fe 3 (PO 4 ) 2 P 2 O 7 The current density of the charge-discharge curve of the first cycle of the C electrode is 0.1C (1 C=129 mAh/g), and the reversible discharge specific capacity of the charge-discharge curve of the C electrode is 100.4mAh/g. Na (Na) 4 Fe 3 (PO 4 ) 2 P 2 O 7 The capacity retention of the/C electrode was 81.3% over 100 cycles at 1C rate. At a high rate of 10C, the reversible capacity of the electrode is only 65.2mAh/g, which is far lower than the electrochemical performance of the S modified material. The detailed data pair is shown in table 1.
Comparative example 3
This comparative example relates to carbon-coated modified polyanionic sodium ion battery cathode material Na 3 V 2 (PO 4 ) 3 and/C, the preparation process comprises the following steps:
s1: mixing: 0.1mol of vanadium pentoxide, 0.3mol of sodium dihydrogen phosphate and 100mL of deionized water were mixed and ground by using a high-energy ball mill. Wherein the ball-to-material ratio, 20:1, the rotating speed is 40Hz, the time is 5H, the solid content is 15%, the particle size range is about 250nm, and the material viscosity is 100Pa.S.
S2: and (3) drying: and (3) vacuum drying the precursor solution in the step S1, wherein the vacuum degree is-0.1 MPa, and obtaining dried precursor powder.
S3: coating: mixing and ball milling the precursor powder dried in the step S2 with citric acid, wherein the ball-to-material ratio is 10:1, ball milling frequency is 30Hz and duration is 10H.
S4: sintering: sintering the powder after ball milling in the step S3, wherein the heating rate is 1 DEG Cmin -1 Preserving heat at 400 deg.C for 3H and 700 deg.C for 12H, and naturally cooling to obtain Na 3 V 2 (PO 4 ) 3 and/C material.
To polyanion Na 3 V 2 (PO 4 ) 3 Mixing the material/C, acetylene black and PVDF according to the mass ratio of 8:1:1 to obtain homogenate, coating black sizing agent on aluminum foil by using a 120um four-sided preparation machine, and drying the film in a vacuum drying oven at 100 ℃ for 10 DEG CHours. The electrode film was punched into a disk having a radius of 0.6mm using a punching machine, and the active material loading was about 2.0mg/cm 2 Sodium metal is used as a counter electrode, and 1mol/L NaClO is used as the counter electrode 4 Ec+dec (1:1vol%) +5% fec was used as an electrolyte, glass fiber was used as a separator, and CR2016 type coin cell was assembled in a glove box. Na (Na) 3 V 2 (PO 4 ) 3 And a charge-discharge curve of the first week of the C electrode, wherein the current density is 0.1C (1C=120 mAh/g), and the reversible specific discharge capacity is 105.8mAh/g. Na (Na) 3 V 2 (PO 4 ) 3 The capacity retention of the/C electrode was 82.1% over 100 cycles at 1C rate. At a high rate of 10C, the reversible capacity of the electrode is 72.1mAh/g, and the electrochemical performance is poorer than that of an S modified material. The detailed data pair is shown in table 1.
TABLE 1 electrochemical Performance test results
Figure SMS_1
The foregoing examples are merely exemplary embodiments of the present invention, which are described in more detail and are not to be construed as limiting the scope of the invention. It should be noted that modifications and improvements can be made by those skilled in the art without departing from the spirit of the invention, and that these obvious alternatives fall within the scope of the invention.

Claims (10)

1. A carbon-sulfur coated polyanionic sodium ion battery positive electrode material, comprising polyanionic positive electrode material particles, characterized in that: the surface of the polyanion positive electrode material particle is a carbon-sulfur coating layer, the thickness of the carbon-sulfur coating layer is 0.1-50 nm, sulfur accounts for 0.1-10% of the total coating layer mass, and the density is 0.1-2.5 g/cm 3 。
2. The carbon sulfur coated polyanionic sodium ion battery positive electrode material according to claim 1, wherein: the general formula of the polyanion positive electrode material is Na a M b (XO 4 ) c Y d Wherein M is Fe, mn,V, cr, ti, ni and/or Co; x is Si and/or P; y is F, P 2 O 7 4- One or two or more of them; a has a value of 0<a< 5.0；0< b< 4.0；0<c< 4.0；0< d< 4.0。
3. The carbon sulfur coated polyanionic sodium ion battery positive electrode material according to claim 1, wherein: the polyanion positive electrode material is NaFePO 4 、NaMnPO 4 、NaNiPO 4 、NaCoPO 4 、Na 2 FeSiO 4 、Na 2 MnSiO 4 、Na 2 CoSiO 4 、Na 2 NiSiO 4 、Na 2 FeP 2 O 7 、Na 2 MnP 2 O 7 、Na 2 CoP 2 O 7 、Na 2 NiP 2 O 7 、Na 4 Fe 3 (PO 4 ) 2 P 2 O 7 、Na 4 Mn 3 (PO 4 ) 2 P 2 O 7 、Na 4 Co 3 (PO 4 ) 2 P 2 O 7 、Na 4 Ni 3 (PO 4 ) 2 P 2 O 7 、Na 3 V 2 (PO 4 ) 3 、Na 4 VMn(PO 4 ) 3 、Na 4 VFe(PO 4 ) 3 、Na 4 MnCr(PO 4 ) 3 、Na 3 MnTi(PO 4 ) 3 、Na 3 VCr(PO 4 ) 3 、Na 3 V 2 (PO 4 ) 2 F 3 、NaFePO 4 F、NaMnPO 4 F、NaCoPO 4 F、NaNiPO 4 F and/or Na 3 (VO x PO 4 ) 2 F 3-2x One or two or more of them.
4. A method for preparing the carbon-sulfur coated polyanionic sodium ion battery positive electrode material according to any one of claims 1 to 3, characterized by comprising the steps of:
s1, mixing materials: the sodium source, the transition metal source and the anion source are mixed according to the stoichiometric ratio Na in the molecular formula a M b (XO 4 ) c Y d Weighing raw materials and uniformly mixing to obtain a primary mixed material;
s2, drying: drying the primary mixed material in the step S1 to obtain dried precursor powder;
s3, coating: mixing and ball milling the precursor powder in the step S2 with a carbon source and a sulfur source to realize coating of a powder interface to obtain coated powder;
s4, sintering: and (3) sintering the coated powder in the step (S3) at high temperature to obtain the carbon-sulfur coated modified polyanion sodium ion battery anode material.
5. The method for preparing the carbon-sulfur coated polyanionic sodium ion battery positive electrode material according to claim 4, wherein the method comprises the following steps: the sodium source is one or more of sodium chloride, sodium sulfate, sodium carbonate, sodium hydroxide, sodium oxalate, sodium citrate, sodium gluconate, sodium dodecylbenzenesulfonate, sodium ethoxide and/or sodium acetylene.
6. The method for preparing the carbon-sulfur coated polyanionic sodium ion battery positive electrode material according to claim 4, wherein the method comprises the following steps: the transition metal source is a Fe source, a Mn source, a V source, a Cr source, a Ti source, a Ni source and/or a Co source;
the Fe source is one or more than two of iron powder, iron oxide, ferric nitrate, ferric sulfate, ferric chloride, ferric citrate, ferric acetate and/or ferric succinate;
the Mn source is one or more than two of manganese oxide, manganese nitrate, manganese acetate, manganese chloride and/or manganese sulfate;
the V source is vanadium oxide and/or ammonium metavanadate;
the Cr source is one or more than two of chromium oxide, sodium chromate and/or chromium hydroxide;
the Ti source is one or more than two of titanium oxide, titanium sulfate and/or titanium sulfate acyl;
the Ni source is one or more than two of nickel oxide, nickel hydroxide and/or nickel sulfate;
the Co source is one or more than two of cobalt oxide, cobalt sulfate and/or cobalt chloride.
7. The method for preparing the carbon-sulfur coated polyanionic sodium ion battery positive electrode material according to claim 4, wherein the method comprises the following steps: the anion source is Si source, P source, F source and/or P source 2 O 7 4- A source;
the Si source is one or more than two of silicic acid, sodium silicate and/or ethyl silicate;
the P source is one or more than two of phosphoric acid, sodium phosphate, sodium hydrogen phosphate, sodium dihydrogen phosphate and/or ammonium dihydrogen phosphate;
the F source is one or more than two of sodium fluoride, ammonium fluoride and/or hydrofluoric acid.
8. The method for preparing the carbon-sulfur coated polyanionic sodium ion battery positive electrode material according to claim 4, wherein the method comprises the following steps:
the addition amount of the carbon source is 0.5-5wt% of the total mass of the solid raw material, the addition amount of the sulfur source is 0.5-2wt% of the total mass of the solid raw material, and the total addition amount of the carbon source and the sulfur source is within 5wt% of the total mass of the solid raw material;
the carbon source is one or more than two of citric acid, glucose, sucrose, starch, maltose, lactose, cyclodextrin, polyethylene glycol, polyvinyl alcohol, carbon powder, carbon nanotube and/or graphene;
the sulfur source is a mercaptan compound, a thiophenol compound and/or a thioether compound, wherein the mercaptan compound is one or more than two of methyl mercaptan, ethyl dithiol, 1-propylmercaptan and/or 1-3 propyldithiol, and the thiophenol compound is one or more than two of o-thiophenol, p-thiophenol and/or thiophenol; the thioether compound is one or more of diallyl sulfide, dibutyl sulfide and/or dimethyl sulfide.
9. The method for preparing the carbon-sulfur coated polyanionic sodium ion battery positive electrode material according to claim 8, wherein the method comprises the following steps:
in the step S1, the mixing mode is liquid phase mixing, semi-solid phase mixing and/or solid phase mixing;
in the step S2, the drying mode is vacuum drying, low-temperature drying, spray drying and/or high-temperature drying;
in the step S3, the precursor powder, the carbon source and the sulfur source are mixed in a ball milling mode, and the weight ratio of the ball materials is 5-20: 1, the rotating speed is 1-50 Hz, and the time length is more than 0.5H;
in the step S4, the sintering temperature is 500-800 ℃, and the temperature rising rate is 0.1-10 degrees Cmin -1 The heat preservation time is longer than 1H.
10. The method for preparing the carbon-sulfur coated polyanionic sodium ion battery positive electrode material according to claim 9, wherein the method comprises the following steps:
in the step S1, the mixing process is assisted by ultrasonic dispersion, mechanical stirring, ball milling and/or sanding; the liquid phase is mixed into a pure solution, and the solid content is 5-40%; the particle size range of solid particles in semi-solid phase mixing and solid phase mixing is 10-300 nm, and the viscosity of materials is 50-400 Pa.S;
in step S2, wherein the vacuum degree of vacuum drying is lower than 0Mpa; the low-temperature drying temperature is lower than 0 ℃; spraying dysphoria air outlet temperature is more than 60 ℃; the high temperature drying temperature is greater than 80 ℃.
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