CN107978738B - Manganese sodium pyrophosphate/carbon composite cathode material and preparation and application thereof - Google Patents
Manganese sodium pyrophosphate/carbon composite cathode material and preparation and application thereof Download PDFInfo
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Abstract
The invention belongs to the field of sodium ion battery anode materials, and particularly discloses a manganese sodium pyrophosphate/carbon composite anode material which is a mixed material of manganese sodium pyrophosphate and carbon, wherein the chemical formula of the manganese sodium pyrophosphate is Na6.24Mn4.88(P2O7)4. The invention also discloses a preparation method and application of the composite cathode material. Na according to the invention6.24Mn4.88(P2O7)4The material has a high-voltage platform of more than 3.8V, an open three-dimensional channel structure is favorable for the diffusion of sodium ions and the reduced lattice distortion, and the multiplying power and the cycle performance of the material are excellent. The preparation method is simple, high in repeatability and low in cost, and has a great commercial application prospect.
Description
Technical Field
The invention relates to the field of sodium ion battery anode materials, in particular to a manganese sodium pyrophosphate composite anode material and a preparation method thereof.
Background
Lithium ion batteries have rapidly occupied the market for portable electronic products (notebook computers, smart mobile devices, tablet computers, etc.) due to their advantages of high energy density, high stability, long life, etc., and have continuously permeated the field of electric vehicles. However, the reserve of lithium resources in the earth crust is low, and the regional distribution is uneven, so that the lithium price of the lithium ion battery is continuously increased in the process of large-scale popularization and application, and the price of the lithium ion battery is high. Therefore, the application of the lithium ion battery in the field of large-scale electricity storage is difficult to realize really. Sodium ion batteries are considered to be an ideal large-scale electricity storage application technology due to abundant sodium resource and environmental friendliness, and therefore have attracted much attention in the world.
During the past decades, researchers have conducted extensive research into positive electrode materials for sodium ion batteries. Among the existing positive electrode material systems, the polyanion-based compound system is considered to be the most commercially promising positive electrode material system for sodium ion batteries. Among polyanion-type compound systems, pyrophosphate system materials have attracted much attention in the world because they have an open ion diffusion channel and are high in structural stability and thermal stability. Na (Na)2MnP2O7Has a ratio of Na to2FeP2O7The higher voltage and theoretical energy density are considered to be a positive electrode material with great application prospect. However, due to Na2MnP2O7The intrinsic electronic conductivity of the lithium ion battery is low, the ion diffusion energy barrier is high, so that the theoretical specific capacity of the lithium ion battery can not be achieved even under low discharge current, and the cycle performance and the rate performance of the lithium ion battery are also extremely poor.
Disclosure of Invention
In order to solve the problems in the prior art, a first object of the present invention is to provide a manganese sodium pyrophosphate/carbon composite cathode material, and to provide a composite cathode material with high voltage and high cycling stability.
The invention also aims to provide a preparation method of the composite cathode material for the sodium-ion battery, which has the advantages of good repeatability, simple operation, environmental friendliness, low cost and industrial application prospect.
The invention also aims to use the prepared material in a sodium ion battery.
Manganese sodium pyrophosphate/carbon composite positive electrode material (also called composite positive electrode material for short in the invention)Material) is a mixed material of sodium manganese pyrophosphate and carbon, and the chemical formula of the sodium manganese pyrophosphate is Na6.24Mn4.88(P2O7)4. Compared with the prior manganese-based sodium-ion battery cathode material, the Na provided by the invention6.24Mn4.88(P2O7)4The material has a high-voltage platform of more than 3.8V, and an open three-dimensional channel structure of the material is beneficial to the diffusion of sodium ions and the reduction of lattice distortion caused by the Zingiber effect, so that the multiplying power and the cycle performance of the material are obviously improved.
The sodium manganese pyrophosphate with the chemical formula is non-stoichiometric sodium manganese pyrophosphate.
The mole ratio of the sodium element, the manganese element and the phosphorus element of the composite anode material is 6.24: 4.88: 8.
Na according to the invention6.24Mn4.88(P2O7)4The crystal form of (A) is a triclinic system, and the space group is P-1.
The composite cathode material is a mixed material of carbon and sodium manganese pyrophosphate, for example, a homogeneous mixture of carbon and sodium manganese pyrophosphate, or the sodium manganese pyrophosphate of the chemical formula is compounded on the surface of carbon.
In the composite positive electrode material, the content of carbon is 3-30 wt%.
The carbon is one or more of conductive carbon black, acetylene black, carbon nanotubes, graphene and reduced graphene oxide.
The invention also provides a preparation method of the manganese pyrophosphate sodium/carbon composite cathode material, which comprises the steps of mixing a sodium source, a manganese source and a phosphorus source according to the proportion of Na, Mn and P elements in the chemical formula, and then calcining for the first time at 250-450 ℃ in an inert atmosphere to obtain an intermediate product; and mixing the intermediate product with a carbon material, and then calcining for the second time at 500-600 ℃ in an inert atmosphere to obtain the composite cathode material.
Under the proportion, a two-step calcination method is adopted, a precursor (intermediate product) of the material is obtained by pre-sintering, and the precursor and the carbon material are mixed (such as ball milling), so that on one hand, the particle size of the material can be reduced, meanwhile, the contact between the carbon material and an active substance is improved, and the carbon material prevents the problem of serious agglomeration of the material in the subsequent calcination process to a certain extent.
The sodium source is preferably soluble in aqueous solution and ionizable to release Na+The compound of (1).
Preferably, the sodium source is one or more of sodium carbonate, sodium bicarbonate, sodium acetate, sodium dihydrogen phosphate and disodium hydrogen phosphate.
The manganese source is preferably soluble in aqueous solution and ionizable to release Mn2+The compound of (1).
Preferably, the manganese source is one or more of manganese dioxide, manganese acetate, manganese oxalate and manganese oxide.
Preferably, the phosphorus source is one or more of monoammonium phosphate, diammonium phosphate, ammonium phosphate, disodium phosphate and monosodium phosphate.
In the invention, the sodium source, the manganese source and the phosphorus source materials in the proportion are preferably mixed by ball milling; a ball milling solvent, such as ethanol, may be added during ball milling; the rotation speed of the ball mill is, for example, 400-500 rpm; the ball milling time is 6-10 h.
And (3) calcining the ball-milled material for the first time in an inert atmosphere (protective atmosphere).
The calcination is carried out at the first calcination temperature, and the prepared intermediate product is mixed with the carbon material to be more beneficial to the subsequent second calcination, and is more beneficial to obtaining the composite cathode material with high phase purity, high crystallinity and better electrical property, especially better cycle performance.
Preferably, the calcination temperature of the first calcination is 300 to 350 ℃.
Preferably, the inert atmosphere is one or more of argon, nitrogen and hydrogen-argon mixed gas.
Under the material proportion and the calcination temperature, the preferable first calcination time is 2-9 h; more preferably 3 to 4 hours.
In the present invention, the first calcination product (intermediate) and the carbon material are mixed, preferably by high energy ball milling.
The intermediate product and the carbon material are preferably ball milled under an inert atmosphere; the rotation speed of the ball milling is 450-550 rpm for example; the ball milling time is, for example, 1 to 2 hours.
Preferably, the carbon material is one or more of conductive carbon black, acetylene black, carbon nanotubes, graphene and reduced graphene oxide.
The adding amount of the carbon material is 3-30% of the mass of the prepared product (theoretical product mass), namely, the carbon material is added according to 3-30% of the weight of the composite cathode material.
The second calcination is carried out under an inert atmosphere similar to the first calcination.
The temperature of the second calcination is controlled within the range, the crystallinity of the material is better, and the electrical property of the obtained material is more excellent.
Preferably, the second calcination temperature is 500 to 550 ℃.
The preferable time of the second calcination is 4-12 h according to the temperatures of the first calcination and the second calcination; further preferably 8 to 12 hours.
According to the preferable preparation method of the composite cathode material, a phosphorus source, a sodium source and a manganese source are mixed in a ball milling mode according to a stoichiometric ratio, and then the mixture is calcined for the first time for 2-9 hours at the temperature of 250-450 ℃ in an inert atmosphere to obtain an intermediate product; then, the intermediate product and the carbon material are subjected to high-energy ball milling and mixing for 0.5-3.5 hours in an inert atmosphere, and then are subjected to secondary calcination for 4-12 hours at 500-600 ℃ in the inert atmosphere to obtain a product Na6.24Mn4.88(P2O7)4a/C composite material.
The invention also provides application of the manganese pyrophosphate sodium/carbon composite cathode material as a cathode active material for preparing a sodium-ion battery cathode.
For example, the Na is added6.24Mn4.88(P2O7)4Mixing the/C composite material with a conductive agent and a binder, and coating the mixture on an aluminum foil to prepare the sodium ion batteryAnd (4) a cell anode. The conductive agent and the binder used may be those known to those skilled in the art. The method for assembling and preparing the positive electrode material of the sodium-ion battery can also refer to the existing method.
For example, the present invention produces Na6.24Mn4.88(P2O7)4Grinding the/C composite material, conductive carbon black and PVDF binder according to the mass ratio of 8: 1, fully mixing, adding NMP to form uniform slurry, coating the slurry on an aluminum foil to be used as a test electrode, taking metal sodium as a counter electrode, and taking 1M NaClO as electrolyte 4100% PC, preparing a sodium half cell and testing the electrochemical performance of the sodium half cell.
The invention also comprises a sodium ion battery assembled by the positive electrode, and the assembling method can adopt the conventional method.
The invention also discloses a method for preparing the carbon-coated spherical vanadium manganese sodium phosphate composite anode material for the sodium-ion battery, and the electrochemical performance of the carbon-coated spherical vanadium manganese sodium phosphate composite anode material is tested.
The invention has the beneficial effects that:
the invention provides Na6.24Mn4.88(P2O7)4the/C composite anode material has a high-voltage platform of more than 3.8V and a stable structure. The material is used for a sodium ion battery, shows good rate performance and cycle performance, and greatly improves the electrochemical performance of the manganese-based polyanionic anode material. For example, the capacity can reach 80mAh g under the multiplying power of 2C-1The above; under the multiplying power of 0.5C, the capacity retention rate of 100 cycles can reach 91.3%.
The preparation method is simple and reliable, environment-friendly, low in cost and good in industrial application prospect.
Drawings
FIG. 1 shows Na obtained in example 16.24Mn4.88(P2O7)4Scanning Electron Micrographs (SEM) of the/C composite cathode material;
FIG. 2 shows Na obtained in example 16.24Mn4.88(P2O7)4/C compositeXRD pattern of the positive electrode material;
FIG. 3 shows that Na was obtained in example 16.24Mn4.88(P2O7)4A multiplying power performance diagram of a sodium ion battery assembled by the/C composite positive electrode material;
FIG. 4 shows the preparation of Na in example 16.24Mn4.88(P2O7)40.5C rate cycle performance diagram of sodium ion battery assembled by/C composite positive electrode material
Detailed Description
The following examples are intended to illustrate the invention in further detail; and the scope of the claims of the present invention is not limited by the examples.
Example 1
1.653g (0.0156mol) of sodium carbonate, 5.980g (0.0244mol) of manganese acetate and 5.282g (0.04mol) of diammonium hydrogen phosphate are taken to be put into a ball milling tank, 68ml of absolute ethyl alcohol is poured into the ball milling tank, the ball milling is carried out for 8h at the rotating speed of 450rpm, after drying, the intermediate product is calcined for 3h at the temperature of 350 ℃ under the argon atmosphere, and the intermediate product is obtained. Carrying out high-energy ball milling (rotating speed 500rpm) on the intermediate product and acetylene black with the mass of 10 wt% of the theoretical product in a ball milling tank in argon atmosphere for 1.5h, and then calcining at 550 ℃ in argon atmosphere for 8h to obtain a product Na6.24Mn4.88(P2O7)4a/C composite material.
Prepared Na6.24Mn4.88(P2O7)4The morphology (SEM) of the/C composite is shown in FIG. 1. The button cell is assembled by the sodium-ion battery composite positive electrode material prepared by the embodiment and a sodium sheet, and as can be seen from fig. 3, the material has excellent rate capability, and even under the rate of 2C, 74.8mAh g is still formed-1The capacity of (c). As can be seen from the multiplying power cycle diagram in FIG. 4, after the battery is cycled for 100 circles at 0.5C, the specific discharge capacity reaches 87.2mAh/g, and the capacity retention rate reaches over 90 percent.
Example 2
1.653g (0.0156mol) of sodium carbonate, 5.980g (0.0244mol) of manganese acetate and 5.282g (0.04mol) of diammonium hydrogen phosphate are taken to be put into a ball milling tank, 68ml of absolute ethyl alcohol is poured into the ball milling tank, the ball milling is carried out for 8h at the rotating speed of 450rpm, after drying, the intermediate product is calcined for 3h at the temperature of 350 ℃ under the argon atmosphere, and the intermediate product is obtained. Will be provided withPerforming high-energy ball milling (500rpm) on the intermediate product and acetylene black with the mass of 10 wt% of the theoretical product in a ball milling tank in argon atmosphere for 1.5h, and then calcining at 500 ℃ in argon atmosphere for 8h to obtain a product Na6.24Mn4.88(P2O7)4a/C composite material.
The button cell assembled by the sodium-ion battery composite positive electrode material prepared by the embodiment and the sodium sheet has a specific capacity of 82mAh/g after 100 cycles under a multiplying power of 0.5C, and the capacity retention rate reaches 85.2%. The 2C multiplying power still has 71.4mAh g-1It shows that the calcination temperature affects the crystallinity of the material, and further affects the electrochemical performance of the material.
Example 3
1.653g (0.0156mol) of sodium carbonate, 5.980g (0.0244mol) of manganese acetate and 5.282g (0.04mol) of diammonium hydrogen phosphate are taken to be put into a ball milling tank, 68ml of absolute ethyl alcohol is poured into the ball milling tank, the ball milling is carried out for 8h at the rotating speed of 450rpm, after drying, the intermediate product is calcined for 3h at the temperature of 350 ℃ under the argon atmosphere, and the intermediate product is obtained. Carrying out high-energy ball milling (500rpm) on the intermediate product and acetylene black with the mass of 5 wt% of the theoretical product in a ball milling tank in argon atmosphere for 1.5h, and then calcining at 600 ℃ in argon atmosphere for 8h to obtain a product Na6.24Mn4.88(P2O7)4a/C composite material. The button cell assembled by the sodium-ion battery composite positive electrode material prepared by the embodiment and the sodium sheet has a specific capacity of 83.4mAh/g after 100 cycles under a multiplying power of 0.5C, and the capacity retention rate reaches 84.7%. The 2C multiplying power still has 70.1mAhg-1。
Example 4
1.653g (0.0156mol) of sodium carbonate, 5.980g (0.0244mol) of manganese acetate and 5.282g (0.04mol) of diammonium hydrogen phosphate are taken to be put into a ball milling tank, 68ml of absolute ethyl alcohol is poured into the ball milling tank, the ball milling is carried out for 8h at the rotating speed of 450rpm, after drying, the intermediate product is calcined for 3h at the temperature of 350 ℃ under the argon atmosphere, and the intermediate product is obtained. Carrying out high-energy ball milling (500rpm) on the intermediate product and acetylene black with the mass of 10 wt% of the theoretical product in a ball milling tank in argon atmosphere for 1.5h, and then calcining at 550 ℃ in argon atmosphere for 12h to obtain a product Na6.24Mn4.88(P2O7)4a/C composite material.
Sodium ion battery prepared by adopting the embodimentThe button cell is assembled by the composite anode material and the sodium sheet, the specific capacity is 84.5mAh/g after 100 cycles under the multiplying power of 0.5C, and the capacity retention rate reaches 85.1%. The 2C multiplying power still has 72.3mAh g-1。
Example 5
2.621g (0.0312mol) of sodium bicarbonate, 5.980g (0.0244mol) of manganese acetate and 5.282g (0.04mol) of diammonium hydrogen phosphate are taken into a ball milling tank, 68ml of absolute ethyl alcohol is poured into the ball milling tank, the ball milling is carried out for 8h at the rotating speed of 450rpm, after drying, the intermediate product is calcined for 4h at the temperature of 300 ℃ under the argon atmosphere, and the intermediate product is obtained. Performing high-energy ball milling (500rpm) on the intermediate product and conductive carbon black with the mass of 10 wt% of the theoretical product in a ball milling tank in argon atmosphere for 1.5h, and then calcining at 550 ℃ in argon atmosphere for 8h to obtain a product Na6.24Mn4.88(P2O7)4a/C composite material. The sodium ion battery composite positive electrode material prepared by the embodiment and a sodium sheet are assembled into a button battery, the specific capacity is 85.7mAh/g after 100 cycles under the multiplying power of 0.5C, and the capacity retention rate is 85.6%. Still has 73.3mAhg at the multiplying power of 2C-1。
Example 6
2.621g (0.0312mol) of sodium bicarbonate, 2.121g (0.0244mol) of manganese dioxide and 5.282g (0.04mol) of diammonium hydrogen phosphate are put into a ball milling tank, 50ml of absolute ethyl alcohol is poured into the ball milling tank, the ball milling is carried out for 8h at the rotating speed of 450rpm, after drying, the intermediate product is calcined for 4h at the temperature of 300 ℃ under the argon atmosphere, and the intermediate product is obtained. Performing high-energy ball milling (500rpm) on the intermediate product and conductive carbon black with the mass of 20 wt% of the theoretical product in a ball milling tank in argon atmosphere for 1.5h, and then calcining at 550 ℃ in argon atmosphere for 8h to obtain a product Na6.24Mn4.88(P2O7)4a/C composite material. The sodium ion battery composite positive electrode material prepared by the embodiment and a sodium sheet are assembled into a button battery, the specific capacity is 83.1mAh/g after 100 cycles under the multiplying power of 0.5C, and the capacity retention rate reaches 84.4%. The 2C multiplying power still has 72mAhg-1。
Example 7
1.653g (0.0156mol) of sodium carbonate, 5.980g (0.0244mol) of manganese acetate and 5.282g (0.04mol) of diammonium hydrogen phosphate are taken into a ball milling tank, 68ml of absolute ethyl alcohol is poured into the ball milling tank, the ball milling is carried out for 8h at the rotating speed of 450rpm, and the mixture is driedAnd calcining the dried product for 3 hours at 350 ℃ in an argon atmosphere to obtain an intermediate product. Performing high-energy ball milling (500rpm) on the intermediate product and a carbon nano tube with the theoretical product mass of 15 wt% in a ball milling tank in argon atmosphere for 1.5h, and then calcining at 500 ℃ in argon atmosphere for 8h to obtain a product Na6.24Mn4.88(P2O7)4a/C composite material.
The button cell assembled by the sodium-ion battery composite positive electrode material prepared by the embodiment and the sodium sheet has a specific capacity of 86.7mAh/g after 100 cycles under a multiplying power of 0.5C, a capacity retention rate of 89.4%, and 76.4mAh g still exists under a multiplying power of 2C-1.
Example 8
1.653g (0.0156mol) of sodium carbonate, 5.980g (0.0244mol) of manganese acetate and 5.282g (0.04mol) of diammonium hydrogen phosphate are taken to be put into a ball milling tank, 68ml of absolute ethyl alcohol is poured into the ball milling tank, the ball milling is carried out for 8h at the rotating speed of 450rpm, after drying, the intermediate product is calcined for 3h at the temperature of 350 ℃ under the argon atmosphere, and the intermediate product is obtained. Carrying out high-energy ball milling (500rpm) on the intermediate product and graphene with the theoretical product mass of 15 wt% in a ball milling tank in argon atmosphere for 1.5h, and then calcining at 500 ℃ in argon atmosphere for 8h to obtain a product Na6.24Mn4.88(P2O7)4a/C composite material.
The button cell assembled by the sodium-ion battery composite positive electrode material prepared by the embodiment and the sodium sheet has a specific capacity of 90.2mAh/g after 100 cycles under a multiplying power of 0.5C, a capacity retention rate of 91.3%, and 80.2mAh g under a multiplying power of 2C-1.
Comparative example 1
This comparative example discusses the effect on the properties of the material obtained at a lower first calcination temperature:
1.653g (0.0156mol) of sodium carbonate, 5.980g (0.0244mol) of manganese acetate and 5.282g (0.04mol) of diammonium hydrogen phosphate are taken to be put into a ball milling tank, 68ml of absolute ethyl alcohol is poured into the ball milling tank, the ball milling is carried out for 8h at the rotating speed of 450rpm, after drying, the intermediate product is calcined for 3h at 150 ℃ under the argon atmosphere, and the intermediate product is obtained. Carrying out high-energy ball milling (500rpm) on the intermediate product and acetylene black with the mass of 10 wt% of the theoretical product in a ball milling tank in argon atmosphere for 1.5h, and then calcining at 550 ℃ in argon atmosphere for 8h to obtain a product Na6.24Mn4.88(P2O7)4a/C composite material. The button cell assembled by the sodium-ion battery composite positive electrode material prepared by the embodiment and the sodium sheet has a specific capacity of 53.4mAh/g after 100 cycles under a multiplying power of 0.5C, and the capacity retention rate reaches 64.2%. The capacity under the rate of 2C is only 43.6mAh g-1。
Comparative example 2
This comparative example discusses the effect on the properties of the material obtained at a higher second calcination temperature:
1.653g (0.0156mol) of sodium carbonate, 5.980g (0.0244mol) of manganese acetate and 5.282g (0.04mol) of diammonium hydrogen phosphate are taken to be put into a ball milling tank, 68ml of absolute ethyl alcohol is poured into the ball milling tank, the ball milling is carried out for 8h at the rotating speed of 450rpm, after drying, the intermediate product is calcined for 3h at the temperature of 350 ℃ under the argon atmosphere, and the intermediate product is obtained. And (3) performing high-energy ball milling (500rpm) on the intermediate product and acetylene black with the mass of 10 wt% of the theoretical product in a ball milling tank in argon atmosphere for 1.5h, and then calcining at 700 ℃ in argon atmosphere for 8h to obtain a product with disordered XRD crystalline phase and more impurities. The button cell assembled by the sodium ion battery composite positive electrode material prepared by the embodiment and the sodium sheet basically has no sodium storage performance under the multiplying power of 0.5C.
Comparative example 3
This comparative example discusses the effect of only one calcination on the properties of the material produced:
1.653g (0.0156mol) of sodium carbonate, 5.980g (0.0244mol) of manganese acetate, 5.282g (0.04mol) of diammonium hydrogen phosphate and acetylene black with the theoretical product mass of 10 wt% are taken to be put into a ball milling tank, 68ml of absolute ethyl alcohol is poured into the ball milling tank, the ball milling is carried out for 8h at the rotating speed of 450rpm, the drying and the calcining are carried out for 8h at the temperature of 550 ℃ under the argon atmosphere, and the product Na is obtained6.24Mn4.88(P2O7)4a/C composite material. The button cell assembled by the sodium-ion battery composite positive electrode material prepared by the embodiment and the sodium sheet has a specific capacity of 36.7mAh/g after 100 cycles under a multiplying power of 0.5C, and the capacity retention rate reaches 44.5%. The material prepared by adopting the one-time sintering process has serious agglomeration and poorer electrochemical performance. The capacity under the multiplying power of 2C is only 26.8mAh g-1。
Claims (7)
1.A preparation method of a manganese pyrophosphate sodium/carbon composite cathode material is characterized by comprising the following steps: according to the formula Na6.24Mn4.88(P2O7)4Mixing a sodium source, a manganese source and a phosphorus source in a ratio of Na, Mn and P by ball milling, and then calcining for the first time at 250-450 ℃ in an inert atmosphere to obtain an intermediate product; mixing the intermediate product with a carbon material, and then calcining for the second time at 500-600 ℃ in an inert atmosphere to obtain the manganese pyrophosphate sodium/carbon composite cathode material;
the carbon material is one or more of conductive carbon black, acetylene black, carbon nanotubes, graphene and reduced graphene oxide;
the composite anode material is a mixed material of sodium manganese pyrophosphate and carbon; the crystal form of the sodium manganese pyrophosphate is a triclinic crystal system, and the space group is P-1;
the carbon is one or more of conductive carbon black, acetylene black, carbon nanotubes, graphene and reduced graphene oxide;
the composite positive electrode material is a homogeneous mixture of carbon and sodium manganese pyrophosphate, or the sodium manganese pyrophosphate is compounded on the surface of the carbon, wherein the content of the carbon is 3-30 wt%.
2. The method for preparing a manganese pyrophosphate sodium/carbon composite positive electrode material according to claim 1, wherein the sodium source is one or more of sodium carbonate, sodium bicarbonate, sodium acetate, sodium dihydrogen phosphate and disodium hydrogen phosphate;
the manganese source is one or more of manganese dioxide, manganese acetate, manganese oxalate and manganese oxide;
the phosphorus source is one or more of ammonium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium phosphate, disodium hydrogen phosphate and sodium dihydrogen phosphate.
3. The method for preparing a manganese pyrophosphate sodium/carbon composite positive electrode material according to claim 1, characterized in that: the adding amount of the carbon material is 3-30% of the mass of the composite anode material.
4. The method for preparing a manganese pyrophosphate sodium/carbon composite positive electrode material according to claim 1, characterized in that: the first calcination time is 2-9 h; the second calcination time is 4-12 h.
5. The method for preparing a manganese pyrophosphate sodium/carbon composite positive electrode material according to claim 1, characterized in that: the inert atmosphere is one or more of argon, nitrogen and hydrogen-argon mixed gas.
6. The method for preparing a manganese pyrophosphate sodium/carbon composite positive electrode material according to claim 1, characterized in that: the intermediate product and the carbon material are ball milled under an inert atmosphere.
7. The application of the sodium manganese pyrophosphate/carbon composite cathode material prepared by the preparation method of any one of claims 1 to 6 is characterized in that: the active material is used as a positive active material for preparing a positive electrode of a sodium-ion battery.
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| CN110289411B (en) * | 2019-07-02 | 2020-08-14 | 中南大学 | Zirconium fluoride manganese sodium phosphate/carbon composite material, positive electrode, sodium ion battery and preparation method thereof |
| CN111446429B (en) * | 2020-03-27 | 2021-12-21 | 珠海冠宇电池股份有限公司 | Poly-polyanion cathode material and preparation method and application thereof |
| CN113328086B (en) * | 2021-08-03 | 2021-11-02 | 南杰智汇(深圳)科技有限公司 | Pyrophosphate composite material, preparation method and application thereof, and sodium ion battery |
| CN113972364B (en) * | 2021-09-30 | 2023-03-24 | 广东邦普循环科技有限公司 | Preparation method of layered carbon-doped sodium iron phosphate cathode material |
| CN116190640B (en) * | 2023-04-17 | 2023-07-25 | 中南大学 | Carbon-coated pyrophosphoric acid polyanion composite material and preparation method and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102856545A (en) * | 2012-09-11 | 2013-01-02 | 清华大学 | Preparation method of micro-nano-grade metal-ion-doped lithium iron phosphate anode material |
| CN106067547A (en) * | 2016-08-10 | 2016-11-02 | 深圳市贝特瑞新能源材料股份有限公司 | Carbon-coated nano 3 SiC 2/graphite alkene cracks carbon-coating composite, preparation method and the lithium ion battery comprising this composite |
| CN106159229A (en) * | 2016-07-28 | 2016-11-23 | 深圳市贝特瑞新能源材料股份有限公司 | Silicon based composite material, preparation method and comprise the lithium ion battery of this composite |
| CN106946238A (en) * | 2017-05-19 | 2017-07-14 | 西南大学 | A kind of vanadium phosphate manganese sodium electrode material and its preparation method and application |
| CN106981641A (en) * | 2017-05-11 | 2017-07-25 | 中南大学 | A kind of carbon coating titanium phosphate manganese sodium composite and preparation method thereof and the application in sodium-ion battery |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB201223473D0 (en) * | 2012-12-28 | 2013-02-13 | Faradion Ltd | Metal-containing compounds |
| CN105161688B (en) * | 2015-09-25 | 2017-11-28 | 中南大学 | A kind of phosphoric acid ferrisodium vanadium phosphate sodium composite of carbon coating and preparation method thereof |
| CN107146883B (en) * | 2017-05-18 | 2019-11-05 | 中南大学 | A kind of pyrophosphoric acid cobalt sodium/carbon anode composite material, preparation and its application of nucleocapsid structure |
| CN107017395B (en) * | 2017-05-22 | 2020-04-21 | 中南大学 | Carbon-coated sodium manganese pyrophosphate @ reduced graphene oxide composite material with sandwich structure and preparation method and application thereof |
-
2017
- 2017-11-13 CN CN201711118657.8A patent/CN107978738B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102856545A (en) * | 2012-09-11 | 2013-01-02 | 清华大学 | Preparation method of micro-nano-grade metal-ion-doped lithium iron phosphate anode material |
| CN106159229A (en) * | 2016-07-28 | 2016-11-23 | 深圳市贝特瑞新能源材料股份有限公司 | Silicon based composite material, preparation method and comprise the lithium ion battery of this composite |
| CN106067547A (en) * | 2016-08-10 | 2016-11-02 | 深圳市贝特瑞新能源材料股份有限公司 | Carbon-coated nano 3 SiC 2/graphite alkene cracks carbon-coating composite, preparation method and the lithium ion battery comprising this composite |
| CN106981641A (en) * | 2017-05-11 | 2017-07-25 | 中南大学 | A kind of carbon coating titanium phosphate manganese sodium composite and preparation method thereof and the application in sodium-ion battery |
| CN106946238A (en) * | 2017-05-19 | 2017-07-14 | 西南大学 | A kind of vanadium phosphate manganese sodium electrode material and its preparation method and application |
Non-Patent Citations (1)
| Title |
|---|
| Porous graphene to encapsulate Na6.24Fe4.88(P2O7)4 as composite cathode materials for Na-ion batteries;Yubin Niu 等;《Royal Society of Chemistry》;20151231;第13120-13122页 * |
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