CN117174865A - Phosphorus-doped carbon-coated sodium ion positive electrode material and preparation method thereof - Google Patents
Phosphorus-doped carbon-coated sodium ion positive electrode material and preparation method thereof Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 72
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 72
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 47
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000007789 gas Substances 0.000 claims abstract description 38
- 239000000758 substrate Substances 0.000 claims abstract description 28
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 claims abstract description 26
- 239000000463 material Substances 0.000 claims abstract description 25
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000010438 heat treatment Methods 0.000 claims abstract description 20
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 18
- 239000011574 phosphorus Substances 0.000 claims abstract description 18
- 239000000843 powder Substances 0.000 claims abstract description 16
- 239000005922 Phosphane Substances 0.000 claims abstract description 15
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910000064 phosphane Inorganic materials 0.000 claims abstract description 15
- 239000012159 carrier gas Substances 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 10
- 239000010405 anode material Substances 0.000 claims abstract description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 10
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 5
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims description 5
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 5
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 5
- 239000011734 sodium Substances 0.000 claims description 5
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 4
- 239000005977 Ethylene Substances 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 4
- 239000002131 composite material Substances 0.000 claims description 3
- 229910052734 helium Inorganic materials 0.000 claims description 3
- 239000001307 helium Substances 0.000 claims description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- 239000011229 interlayer Substances 0.000 abstract description 3
- 230000037427 ion transport Effects 0.000 abstract 1
- 238000000576 coating method Methods 0.000 description 14
- 239000011248 coating agent Substances 0.000 description 13
- 239000011247 coating layer Substances 0.000 description 7
- 239000013078 crystal Substances 0.000 description 7
- 239000010410 layer Substances 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 239000003792 electrolyte Substances 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 230000006978 adaptation Effects 0.000 description 2
- 229910003481 amorphous carbon Inorganic materials 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000010894 electron beam technology Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- -1 carbon tubes Chemical compound 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 230000005281 excited state Effects 0.000 description 1
- 238000010574 gas phase reaction Methods 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000000386 microscopy Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920000447 polyanionic polymer Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000004627 transmission electron microscopy Methods 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
Classifications
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- 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
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- Chemical Vapour Deposition (AREA)
Abstract
The invention discloses a phosphorus-doped carbon-coated sodium ion positive electrode material and a preparation method thereof, comprising the following steps: s1: the sodium-electricity layered oxide positive electrode material powder is put on a substrate in a cavity of PECVD equipment, and the height of the substrate is adjusted to enable the sodium-electricity layered oxide positive electrode material powder to be positioned in a gas plasma reaction area; s2: vacuumizing the PECVD equipment to be less than 20Torr, and heating the substrate to 200-400 ℃; s3: introducing a mixed gas of carbon source gas, carrier gas and phosphane into a cavity of PECVD equipment, heating the PECVD equipment, igniting microwave plasma, adjusting microwave power, maintaining the power within the range of 1000-3500W, and reacting for 1-10h; s4: stopping introducing gas and heating PECVD equipment, introducing nitrogen to make the cavity reach normal pressure when the temperature of the substrate is reduced to below 100 ℃, and taking out the powder material to obtain the phosphorus-doped carbon-coated sodium ion anode material. Phosphorus doping increases the interlayer spacing of carbon, which is more conducive to sodium ion transport.
Description
Technical Field
The invention relates to the technical field of lithium batteries, in particular to a phosphorus-doped carbon-coated sodium ion positive electrode material and a preparation method thereof.
Background
In the positive electrode material of the sodium ion battery, the layered metal oxide is easy to synthesize and has higher capacity. But the cycle life is poor due to the fact that the surface of the material is easy to react with the electrolyte and undergo structural transformation. The common improvement method is to coat the oxide, reduce the contact area with the electrolyte and further weaken the side reaction. However, the oxide coating layer is an insulator, the electronic conductivity is poor, and after the oxide is coated on the surface, the conductivity of the layered oxide sodium-electricity positive electrode material is reduced, so that the rate performance is reduced. And the oxide coating is difficult to realize uniform coating, and generally presents discontinuous particle coating layers, and the surface of the positive electrode material is still exposed in a larger proportion area and directly reacts with electrolyte.
In the polyanion sodium-electricity positive electrode material, carbon coating is a common means for improving the conductivity of the material, and the common method for carbon coating is to mix carbon-containing organic matters such as glucose, sucrose and the like with the positive electrode material, and then carbonize the mixture at a high temperature of more than 500 ℃ under the protection of inert atmosphere, so as to realize the carbon coating on the surface of the material. However, the layered oxide is susceptible to oxidation-reduction reaction with a carbon source at high temperature, resulting in a crystal structure failure, and uniform carbon coating is difficult to obtain. The common carbon coating method for the layered oxide material is to physically mix the layered oxide material with elemental carbon, namely carbon tubes, carbon black, carbon fibers and the like to realize surface coating, but the physically mixed coated carbon has the defects of loose contact, incomplete coating and the like, and is difficult to effectively improve the conductivity and interface stability of the positive electrode material.
Disclosure of Invention
The invention aims to: the invention aims to provide a phosphorus-doped carbon-coated sodium ion positive electrode material which can increase the interlayer spacing of carbon and is beneficial to sodium ion transmission and a preparation method thereof.
The technical scheme is as follows: in order to achieve the above object, the present invention provides a phosphorus-doped carbon-coated sodium ion positive electrode material and a method for preparing the same, comprising the steps of:
s1: the sodium-electricity layered oxide positive electrode material powder is put on a substrate in a cavity of PECVD equipment, and the height of the substrate is adjusted to enable the sodium-electricity layered oxide positive electrode material powder to be positioned in a gas plasma reaction area;
s2: vacuumizing the PECVD equipment to be less than 20Torr, and heating the substrate to 200-400 ℃;
s3: introducing a mixed gas of carbon source gas, carrier gas and phosphane into a cavity of PECVD equipment, heating the PECVD equipment, igniting microwave plasma, adjusting microwave power, maintaining the power within the range of 1000-3500W, and reacting for 1-10h;
s4: stopping introducing gas and heating PECVD equipment, introducing nitrogen to make the cavity reach normal pressure when the temperature of the substrate is reduced to below 100 ℃, and taking out the powder material to obtain the phosphorus-doped carbon-coated sodium ion anode material.
Further, the surface of the phosphorus-doped carbon-coated sodium ion positive electrode material is uniformly coated with a phosphorus-containing carbon layer with the thickness of 1-10 nm.
Further, the phosphorus-containing carbon layer accounts for 0.5-3% of the mass of the composite material, and the phosphorus content in the carbon layer is 0.01-2%.
Further, the expression of the phosphorus-doped carbon-coated sodium ion positive electrode material is Na x Ma y Mb z Mc v Md w O 2 C, wherein 1 is greater than or equal to x, y, z, v, and w is greater than or equal to 0.
Further, ma, mb, mc, md is any one of Fe, mn, cu, ni.
Preferably, the phosphorus-doped carbon-coated sodium ion positive electrode material is NaNi 1/3 Fe 1/3 Mn 1/3 O 2 -C。
Preferably, the phosphorus-doped carbon-coated sodium ion positive electrode material is Na 0.9 Fe 0.22 Cu 0.3 Mn 0.48 O-C。
Further, the carbon source gas is one or more of methane, ethane, acetylene, ethylene and propylene; the carrier gas is one or more of hydrogen, argon, nitrogen and helium.
Further, the carbon source gas: phosphane: carrier gas = 1-10:1:3-20.
PECVD is a common method used in the semiconductor industry for preparing films, and the principle is that a gaseous precursor is ionized under the action of plasma to form active groups in an excited state, and the active groups reach the surface of a material to be coated through diffusion, so that chemical reaction is carried out to deposit the active groups on the surface of the material to be coated. PECVD has the outstanding advantage of low reaction temperature compared with other gas phase reactions.
The beneficial effects are that: 1. the invention designs a layered oxide sodium-electricity positive electrode material with a carbon coating layer, which has the advantages of good interface stability, good conductivity, less side reaction with the surface of electrolyte, and obviously improved cycle performance and multiplying power performance compared with an uncoated material and an oxide coated material.
2. The invention develops a low-temperature vapor deposition method for coating surface amorphous carbon, which realizes uniform coating of the surface of a layered oxide positive electrode material without damaging the structure of the positive electrode material.
3. According to the invention, the phosphorus-containing reactant is introduced into the coating gas source, so that the phosphorus doping in the carbon coating layer is realized, the interlayer spacing of carbon can be increased, and the sodium ion transmission is facilitated.
Drawings
Fig. 1 is an example phosphorus doped carbon coated sodium ion positive electrode material.
Detailed Description
A phosphorus-doped carbon-coated sodium ion positive electrode material and a preparation method thereof comprise the following steps:
s1: the sodium-electricity layered oxide positive electrode material powder is put on a substrate in a cavity of PECVD equipment, and the height of the substrate is adjusted to enable the sodium-electricity layered oxide positive electrode material powder to be positioned in a gas plasma reaction area;
s2: vacuumizing the PECVD equipment to be less than 20Torr, and heating the substrate to 200-400 ℃;
s3: introducing a mixed gas of carbon source gas, carrier gas and phosphane into a cavity of PECVD equipment, heating the PECVD equipment, igniting microwave plasma, adjusting microwave power, maintaining the power within the range of 1000-3500W, and reacting for 1-10h; the carbon source gas is one or more of methane, ethane, acetylene, ethylene and propylene; the carrier gas is one or more of hydrogen, argon, nitrogen and helium. The carbon source gas: phosphane: carrier gas = 1-10:1:3-20.
S4: stopping introducing gas and heating PECVD equipment, introducing nitrogen to make the cavity reach normal pressure when the temperature of the substrate is reduced to below 100 ℃, and taking out the powder material to obtain the phosphorus-doped carbon-coated sodium ion positive electrode material shown in figure 1. The surface of the phosphorus-doped carbon-coated sodium ion positive electrode material is uniformly coated with a phosphorus-containing carbon layer with the thickness of 1-10 nm. The phosphorus-containing carbon layer accounts for 0.5-3% of the composite material in mass ratio, and the phosphorus content in the carbon layer is 0.01-2%. The expression of the phosphorus-doped carbon-coated sodium ion positive electrode material is Na x Ma y Mb z Mc v Md w O 2 C, wherein 1 is greater than or equal to x, y, z, v, and w is greater than or equal to 0.Ma, mb, mc, md is any one of Fe, mn, cu, ni. C is a phosphorus doped carbon coating.
Example 1
Will be loaded with NaNi 1/3 Fe 1/3 Mn 1/3 O 2 Placing a crucible of positive electrode powder material on a substrate in a cavity of Plasma Enhanced Chemical Vapor Deposition (PECVD) equipment, vacuumizing a reaction cavity to below 10Torr, heating the substrate to 300 ℃, introducing mixed gas of methane, hydrogen and phosphane, wherein the proportion of methane is 5%, the proportion of phosphane is 0.5%, the gas flow rate is 50sccm, maintaining the vacuum degree at 20Torr, igniting microwave plasma, adjusting the microwave power to 1000W, the reaction time to 4h, stopping introducing gas, closing the plasma and a heating source, removing the vacuum after the temperature of the substrate is reduced to below 100 ℃, taking out the crucible after introducing nitrogen, and obtaining the phosphorus-doped carbon-coated NaNi 1/3 Fe 1/3 Mn 1/3 O 2 The XRD characterization proves that the material structure is not changed obviously, and the TEM characterization shows that the surface of the material is coated with a layer of amorphous carbon with the thickness of about 5nm, and the phosphorus content of the coating layer is about 1%.
XRD stands for X-ray Diffraction (X-ray Diffraction), a technique used for analyzing the crystal structure. XRD determines information on crystal structure, lattice parameter, and crystal orientation by measuring X-ray diffraction patterns in the material. As X-rays pass through the material, they are scattered by atoms in the crystal and form a specific diffraction pattern. By analyzing these diffraction patterns, the crystal structure of the material can be deduced.
TEM stands for transmission electron microscopy (Transmission Electron Microscope), a high resolution microscopy technique. TEM uses an electron beam that passes through a sample to observe the details of the interior and surface of the sample. By projecting an electron beam on a sample and collecting a transmitted electron image, high resolution information about the sample can be obtained. TEM is capable of providing detailed information about the crystal structure, grain size, interface characteristics, etc. of a material.
Example 2
Will be loaded with NaNi 1/3 Fe 1/3 Mn 1/3 O 2 Placing a crucible of positive electrode material powder on a substrate in a cavity of a MW-PECVD device, vacuumizing a reaction cavity to below 10Torr, heating the substrate to 400 ℃, introducing a mixed gas of ethylene, hydrogen and phosphane, wherein the ratio of ethane gas is 10%, the ratio of phosphane is 1%, the gas flow rate is 100sccm, maintaining the vacuum degree of 20Torr, igniting microwave plasma, adjusting the microwave power to 1800W, reacting for 8 hours, stopping introducing gas, closing the plasma and a heating source, releasing vacuum when the temperature of the substrate is reduced to below 100 ℃, introducing nitrogen, and taking out the crucible to obtain the phosphorus-doped carbon-coated NaNi 1/3 Fe 1/3 Mn 1/3 O 2 -C positive electrode material having a carbon content of 3% and a phosphorus content of about 1% in the coating layer.
Example 3
Will be loaded with NaNi 0.23 Fe 0.33 Cu 0.1 Mn 0.34 O 2 Placing a crucible of positive electrode material powder on a substrate in a cavity of PECVD equipment, vacuumizing a reaction cavity to below 20Torr, heating the substrate to 200 ℃, introducing mixed gas of propylene, argon and phosphane, wherein the ratio of propylene gas is 10%, the ratio of phosphane is 1%, the gas flow rate is 50sccm, maintaining the vacuum degree to 30Torr, igniting microwave plasma, adjusting the microwave power to 1000W, reacting for 4 hours, stopping introducing gas, closing the plasma and a heating source, removing vacuum when the temperature of the substrate is reduced to below 100 ℃, introducing nitrogen, and taking out the crucible to obtain the phosphorus-doped carbon-coated NaNi 1/3 Fe 1/3 Mn 1/3 O 2 -C positive electrodeThe material had a carbon content of 1% and the coating had a phosphorus content of about 0.5%.
Example 4
Will be loaded with Na 0.9 Fe 0.22 Cu 0.3 Mn 0.48 O 2 Placing a crucible of anode material powder on a substrate in a cavity of microwave plasma enhanced chemical vapor deposition (MW-PECVD) equipment, vacuumizing a reaction cavity to below 20Torr, heating the substrate to 300 ℃, introducing mixed gas of acetylene, hydrogen and phosphane, wherein the proportion of acetylene gas is 5%, the proportion of phosphane is 1%, the gas flow rate is 80sccm, maintaining the vacuum degree at 50Torr, igniting microwave plasma, adjusting the microwave power to 2600W, reacting for 4 hours, stopping introducing gas, closing the plasma and a heating source, removing the vacuum after the temperature of the substrate is reduced to below 100 ℃, taking out the crucible after introducing nitrogen gas, and obtaining the phosphorus-doped carbon-coated NaNi 1/3 Fe 1/3 Mn 1/3 O 2 -C positive electrode material having a carbon content of 1% and a phosphorus content of about 0.8% in the coating layer.
Comparative example 1
As a comparative example, the phosphorus-doped carbon-coated sodium ion positive electrode materials prepared in examples 1 to 4, uncoated NaNi 1/3 Fe 1/3 Mn 1/3 O 2 And 2% alumina coated NaNi 1/3 Fe 1/3 Mn 1/3 O 2 The positive electrode materials are prepared into 3 soft package batteries with the capacity of 10Ah, and the other materials have the same formula and cell design. The battery is tested for normal temperature cycle performance (1.5-3.9V) and rate discharge performance after being taken off line, and the results are shown in the following table, and the rate performance and cycle performance of the carbon coated material cell are obviously higher than those of the uncoated material.
From the table, the cycle performance and the rate performance of the lithium battery are obviously improved by using the battery with the carbon coated sodium-electricity material.
The foregoing is only a preferred embodiment of the invention, it being noted that: it will be apparent to those skilled in the art that various modifications and adaptations can be made without departing from the principles of the present invention, and such modifications and adaptations are intended to be comprehended within the scope of the invention.
Claims (7)
1. The phosphorus-doped carbon-coated sodium ion positive electrode material and the preparation method thereof are characterized by comprising the following steps:
s1: the sodium-electricity layered oxide positive electrode material powder is put on a substrate in a cavity of PECVD equipment, and the height of the substrate is adjusted to enable the sodium-electricity layered oxide positive electrode material powder to be positioned in a gas plasma reaction area;
s2: vacuumizing the PECVD equipment to be less than 20Torr, and heating the substrate to 200-400 ℃;
s3: introducing a mixed gas of carbon source gas, carrier gas and phosphane into a cavity of PECVD equipment, heating the PECVD equipment, igniting microwave plasma, adjusting microwave power, maintaining the power within the range of 1000-3500W, and reacting for 1-10h;
s4: stopping introducing gas and heating PECVD equipment, introducing nitrogen to make the cavity reach normal pressure when the temperature of the substrate is reduced to below 100 ℃, and taking out the powder material to obtain the phosphorus-doped carbon-coated sodium ion anode material.
2. The phosphorus-doped carbon-coated sodium ion positive electrode material and the preparation method thereof according to claim 1, wherein the surface of the phosphorus-doped carbon-coated sodium ion positive electrode material is uniformly coated with a phosphorus-containing carbon layer with the thickness of 1-10 nm.
3. The phosphorus-doped carbon-coated sodium ion positive electrode material and the preparation method thereof according to claim 2, wherein the phosphorus-containing carbon layer accounts for 0.5-3% of the composite material by mass, and the phosphorus content in the carbon layer is 0.01-2%.
4. The phosphorus-doped carbon-coated sodium ion positive electrode material and the preparation method thereof according to claim 1, wherein the composition of the phosphorus-doped carbon-coated sodium ion positive electrode material is Na x Ma y Mb z Mc v Md w O 2 C, wherein 1 is greater than or equal to x, y, z, v, and w is greater than or equal to 0.
5. The phosphorus-doped carbon-coated sodium ion positive electrode material and the preparation method thereof according to claim 4, wherein Ma, mb, mc, md is any one of Fe, mn, cu, ni.
6. The phosphorus-doped carbon-coated sodium ion positive electrode material and the preparation method thereof according to claim 1, wherein the carbon source gas is one or more of methane, ethane, acetylene, ethylene and propylene; the carrier gas is one or more of hydrogen, argon, nitrogen and helium.
7. The phosphorus-doped carbon-coated sodium ion positive electrode material and the preparation method thereof according to claim 1, wherein the carbon source gas is: phosphane: carrier gas = 1-10:1:3-20.
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