CN106898754B - Application of heteroatom in preparation of carbon-phosphorus material of lithium-phosphorus battery, material and preparation method thereof - Google Patents
Application of heteroatom in preparation of carbon-phosphorus material of lithium-phosphorus battery, material and preparation method thereof Download PDFInfo
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- CN106898754B CN106898754B CN201710262086.9A CN201710262086A CN106898754B CN 106898754 B CN106898754 B CN 106898754B CN 201710262086 A CN201710262086 A CN 201710262086A CN 106898754 B CN106898754 B CN 106898754B
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- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
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Abstract
The invention discloses an application of hetero atoms in preparing a carbon-phosphorus material of a lithium-phosphorus battery, the material and a preparation method thereof, coconut shell carbon and/or Keqin black are used as a carbon source, and P is2O5And/or purple phosphorus is used as a phosphorus source and is doped with hetero atoms to prepare the carbon-phosphorus composite material for the lithium-phosphorus battery.
Description
Technical Field
The invention relates to a lithium phosphorus battery technology, in particular to application of heteroatoms in preparation of a carbon phosphorus material of a lithium phosphorus battery, the material and a preparation method thereof.
Background
The establishment of a clean and efficient energy storage system has great practical significance for promoting the social and economic progress and sustainable development of the country. The development of power batteries with high specific energy and the improvement of the proportion of clean energy in the energy structure of China are urgent requirements for the development of the economy and the society. Therefore, the development of the zero-emission electric automobile is placed in a strategic position of priority development. However, the specific capacity of the existing lithium battery positive electrode material is low (less than 200mAh/g), the overall specific energy of the battery is less than 300Wh/kg, and meanwhile, the specific energy is difficult to be greatly improved through material preparation and process optimization due to the limitation of the theoretical capacity of the material. The existing lithium battery has low specific energy, so that the endurance mileage of the electric automobile is short, and the bottleneck restricting the rapid development of the industry is formed.
The energy density of lithium ion batteries is generally limited by the active material of the positive electrode, and most of the positive electrode materials of the lithium ion batteries are single-electron or embedded reaction materials with less single-electron, so that the positive electrode materials have smaller specific capacity. At present, commercial anode materials such as LiCoO2, LiNiO2, LiMnO2, LiFePO4 and the like are difficult to meet the requirements of high-specific-capacity lithium ion batteries due to low theoretical specific capacity (< 200 mAh/g). In the organic electrolyte, the nonmetal active substance with small molecular weight has higher oxidation-reduction potential and multi-electron reaction characteristics, so the nonmetal active substance has larger theoretical specific capacity and is very suitable to be used as the anode material of the lithium ion battery. For example, the elemental phosphorus has low molecular weight and 3-electron reaction characteristics, and the theoretical capacity of the elemental phosphorus is 2596mAh/g, which is 30% higher than the theoretical specific capacity of elemental sulfur. If elementary phosphorus is used as a positive active material of a secondary battery and is combined with lithium metal or lithium metal alloy to form a novel secondary battery system, the energy density is higher.
The novel lithium-phosphorus battery system can well meet the requirement of electric automobiles on high-specific-energy power batteries, and therefore, the novel lithium-phosphorus battery system becomes a hot spot of competitive research of scientists at home and abroad in recent years. The theoretical specific capacity of the negative electrode lithium is 3860mAh/g, and the theoretical specific capacity of the positive electrode phosphorus is 2596mAh/g, so that the theoretical specific energy of the lithium-phosphorus battery reaches 2600Wh/kg, which is 8-10 times of that of the traditional lithium battery and is the highest in the known lithium battery system; and the high rate discharge performance is excellent; in addition, the phosphorus resource is abundant, cheap and environment-friendly. Therefore, lithium phosphorus battery systems are becoming the first choice for the development of high specific energy power batteries.
However, in practical application and production, due to the difficulty in material synthesis and low conductivity, the cycle life of the material is poor, the capacity attenuation is fast, the rate capability is poor, the first charge-discharge efficiency is low, and the low-temperature performance is poor. Therefore, a method for preparing and modifying the lithium-phosphorus battery cathode material is urgently sought. Firstly, the traditional method is used, the load capacity of phosphorus is low, secondly, the phosphorus loaded in the battery circulation process is easy to react with electrolyte to form a multi-phosphorus compound, and the capacity and the circulation stability of the lithium phosphorus battery are reduced. The application of elemental phosphorus in lithium ion battery electrode Materials is reported for the first time to be prepared into active Materials by compounding expensive black phosphorus and conductive graphite by a high-pressure ball milling method, (Advanced Materials,2007, 19, 2465-2468). The red phosphorus and carbon material or conductive polymer composite material is not higher than 550mAh/g (CN101533900A) after 60 times of circulation. In the synthetic active materials, the preparation conditions of black phosphorus are harsh, the price is high, and the cycle performance of the red phosphorus battery is not high, so that the defects exist.
Disclosure of Invention
In order to solve the defects of the prior art, the invention provides an application of heteroatoms in preparation of a carbon phosphorus material of a lithium phosphorus battery, the material and a preparation method thereof.
The technical scheme of the invention is as follows: the application of the heteroatom in the preparation of the carbon-phosphorus composite material of the lithium-phosphorus battery, wherein the heteroatom is at least one of B, N, F, Si, S, Cl, As, Se, Br, Te and I.
The invention also aims to provide a lithium-phosphorus battery composite material which takes coconut shell carbon and/or Keqin black as a carbon source and P2O5And/or purple phosphorus is a phosphorus source and is doped with at least one of hetero atoms B, N, F, Si, S, Cl, As, Se, Br, Te and I.
The invention further provides a method for preparing the lithium-phosphorus battery composite material, which comprises the following steps of (1) weighing a carbon source, a phosphorus source and a heteroatom source according to the mass ratio of 0-1: 0-0.1, adding the carbon source, the phosphorus source and the heteroatom source into a reaction kettle, adding a dispersing agent and a reaction medium, reacting at the temperature of 60-120 ℃ for 4-12 hours; (2) taking out the reaction product obtained in the step (1), and mechanically stirring uniformly for 8-24 hours; (3) washing the stirred reaction product obtained in the step (2) with deionized water until the pH value is 7-9; (4) placing the product washed in the step (3) in a forced air drying oven, and carrying out forced air drying for 8-16 hours at the temperature of 60-100 ℃ to obtain a precursor; (5) and (3) mechanically ball-milling the precursor in the step (4) for 2-12 hours, then placing the precursor in a muffle furnace, and sintering the precursor in a nitrogen or argon atmosphere at 400-600 ℃ for 6-15 hours to obtain the heteroatom-doped lithium-phosphorus battery composite material.
Further improvements of the invention include:
the dispersant is at least one of polyacrylic acid, ammonium polymethacrylate and ammonium citrate, and the adding amount of the dispersant is lwt-20 wt% of the total mass of the carbon source, the phosphorus source and the heteroatom source.
The reaction medium is at least one of ethylene glycol and isopropanol, and the adding amount of the reaction medium is l00 wt-200 wt% of the total mass of the carbon source, the phosphorus source and the heteroatom source.
The invention has the advantages of simple synthesis process, high specific capacity, good cycle performance and low process cost.
Drawings
Fig. 1 is a graph of the cycle capacity of 0.1C at room temperature for batteries made of different materials.
Detailed Description
The present invention will be described in detail with reference to examples.
Example 1
Prepared from coconut shell charcoal and P2O5Weighing raw materials into a reaction kettle according to the molar ratio of C, P and S being 0.6:0.4:0.015, and then adding 10% of polyacrylic acid serving as a dispersing agent and l00 wt% of ethylene glycol serving as a reaction medium; putting the reaction kettle filled with the mixed solution into a muffle furnace for reaction at the reaction temperature of 60 ℃ for 12 hours; taking out the reaction product, and stirring and mixing for 8 hours; taking out the stirred product, washing the stirred product until the pH value is 8, putting the product into a forced air drying oven, and carrying out forced air drying for 16 hours at the temperature of 60 ℃ to obtain a precursor; and mechanically ball-milling the obtained precursor for 10 hours, then placing the precursor into a muffle furnace, and sintering the precursor for 13 hours at 450 ℃ in a nitrogen atmosphere to obtain the product with higher phase purity.
Battery fabrication and testing
0.8g of the positive active material prepared by the method is weighed, 0.19g of acetylene black is added, 0.1g of polyvinylidene fluoride adhesive is dissolved in N-N dimethyl pyrrolidone, the mixture is uniformly mixed to form slurry, the slurry is uniformly coated on aluminum foil, a metal embedded sheet is used as a counter electrode, celgard2400 is used as a diaphragm, lmol/L LIPF6/EC: DEC (1:1) is used as electrolyte in an argon atmosphere glove box, a CR2016 type button cell is assembled, and a testing instrument is a LANDCT2001 type cell testing system. The battery was subjected to a charge-discharge cycle test in a voltage range of 1.0V to 3.0V.
Example 2
Prepared from Keqin black, purple phosphorus and TeO2、As2O3Weighing raw materials according to the weight ratio of C, P, Te and As being 0.5:0.5:0.01:0.01, putting the raw materials into a reaction kettle, and then adding 15% of ammonium polymethacrylate and 20 wt% of isopropanol serving As a reaction medium; putting the reaction kettle filled with the mixed solution into a muffle furnace for reaction at the temperature of 80 ℃ for 10 hours; taking out the reaction product, and stirring and mixing for 10 hours; getWashing the stirred product until the pH value is 7, putting the product into a forced air drying oven, and carrying out forced air drying at 70 ℃ for 12 hours to obtain a precursor; and mechanically ball-milling the obtained precursor for 6 hours, then placing the precursor into a muffle furnace, and sintering the precursor for 11 hours at 500 ℃ in an argon atmosphere to obtain the product with higher phase purity.
The procedure for making and testing the battery was the same as in example 1
Example 3
The coconut shell charcoal and Keqin black are mixed according to a ratio of 1:1 to form mixed carbon P2O5Elemental substance S, SiO2、SeO2Weighing raw materials according to the weight ratio of C, P, S, Si, Se, 0.45, 0.55, 0.01 and 0.01 into a reaction kettle, and then adding a mixed solution of 12 percent of ammonium citrate as a dispersing agent and 20 percent of ethylene glycol and 5 percent of isopropanol as a reaction medium, i.e. 20wt percent of mixed solution; putting the reaction kettle filled with the mixed solution into a muffle furnace to react for 8 hours at the temperature of 100 ℃; taking out the reaction product, and stirring and mixing for 8 hours; taking out the stirred product, washing the stirred product until the pH value is 9, putting the product into a forced air drying oven, and carrying out forced air drying at 80 ℃ for 10 hours to obtain a precursor; and mechanically ball-milling the obtained precursor for 4 hours, then placing the precursor into a muffle furnace, and sintering the precursor for 8 hours at 550 ℃ in a nitrogen atmosphere to obtain the product with higher phase purity. The procedure for making and testing the battery was the same as in example 1
Example 4
Mixing coconut shell charcoal and Keqin black according to a ratio of 2:1 to form mixed carbon, purple phosphorus and SiO2, weighing the raw materials according to a ratio of C to P to Si of 0.4:0.6:0.02, putting the raw materials into a reaction kettle, and adding a mixture of 10% of polyacrylic acid and 8% of ammonium citrate as well as a reaction medium of 4:6 of ethylene glycol and isopropanol, wherein the mixture is mixed with 50: 50 wt%; putting the reaction kettle filled with the mixed solution into a muffle furnace to react for 4 hours at the temperature of 120 ℃; taking out the reaction product, and stirring and mixing for 10 hours; taking out the stirred product, washing the stirred product until the pH value is 8, putting the product into a forced air drying oven, and carrying out forced air drying for 8 hours at 90 ℃ to obtain a precursor; and mechanically ball-milling the obtained precursor for 2 hours, then placing the precursor into a muffle furnace, and sintering the precursor for 6 hours at 600 ℃ in an argon atmosphere to obtain the product with higher phase purity.
The procedure for making and testing the battery was the same as in example 1
Comparative example 1
Coconut shell charcoal and purple phosphorus are weighed according to the ratio of 0.5:0.5, and the preparation method and the battery manufacturing and testing process are the same as those of the example 1. FIG. 1 is a graph of the cycling capacity of 0.1C at room temperature for batteries made of different materials
Table 1 results of testing cells fabricated in examples and comparative columns at room temperature
From table 1 and fig. 1, it can be seen that the specific capacity and the cycling stability at 0.1 multiplying power of the batteries manufactured by the synthetic materials of examples 1 to 4 of the invention at room temperature are higher than those of comparative example 1. The heteroatom doped carbon phosphorus material prepared by the invention can effectively improve the specific capacity and the cycling stability of the lithium phosphorus battery, and lays a foundation for realizing the large-scale market application of the lithium phosphorus battery.
The foregoing shows and describes the general principles and broad features of the present invention and advantages thereof. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (4)
1. A lithium phosphorus battery composite characterized by:
the preparation method of the lithium-phosphorus battery composite material comprises the following steps,
(1) weighing a carbon source, a phosphorus source and a heteroatom source according to the mass ratio of 0-1: 0-0.1, adding the carbon source, the phosphorus source and the heteroatom source into a reaction kettle, adding a dispersing agent and a reaction medium, reacting at the temperature of 60-120 ℃ for 4-12 hours;
(2) taking out the reaction product obtained in the step (1), and mechanically stirring uniformly for 8-24 hours;
(3) washing the stirred reaction product obtained in the step (2) with deionized water until the pH value is 7-9;
(4) placing the product washed in the step (3) in a forced air drying oven, and carrying out forced air drying for 8-16 hours at the temperature of 60-100 ℃ to obtain a precursor;
(5) mechanically ball-milling the precursor in the step (4) for 2-12 hours, then placing the precursor in a muffle furnace, and sintering the precursor in a nitrogen or argon atmosphere at 400-600 ℃ for 6-15 hours to obtain a heteroatom-doped lithium-phosphorus battery composite material;
in the step (1), the carbon source is coconut shell carbon and/or Keqin black, and the phosphorus source is P2O5And/or purple phosphorus, wherein the heteroatom source is at least one of heteroatoms of B, N, F, Si, S, Cl, As, Se, Br, Te and I.
2. A method for preparing a lithium phosphorus battery composite material according to claim 1, characterized by the following steps:
(1) weighing a carbon source, a phosphorus source and a heteroatom source according to the mass ratio of 0-1: 0-0.1, adding the carbon source, the phosphorus source and the heteroatom source into a reaction kettle, adding a dispersing agent and a reaction medium, reacting at the temperature of 60-120 ℃ for 4-12 hours;
(2) taking out the reaction product obtained in the step (1), and mechanically stirring uniformly for 8-24 hours;
(3) washing the stirred reaction product obtained in the step (2) with deionized water until the pH value is 7-9;
(4) placing the product washed in the step (3) in a forced air drying oven, and carrying out forced air drying for 8-16 hours at the temperature of 60-100 ℃ to obtain a precursor;
(5) mechanically ball-milling the precursor in the step (4) for 2-12 hours, then placing the precursor in a muffle furnace, and sintering the precursor in a nitrogen or argon atmosphere at 400-600 ℃ for 6-15 hours to obtain a heteroatom-doped lithium-phosphorus battery composite material;
in the step (1), the carbon source is coconut shell carbon and/or Keqin black, and the phosphorus source is P2O5And/or purple phosphorus, wherein the heteroatom source is at least one of heteroatoms of B, N, F, Si, S, Cl, As, Se, Br, Te and I.
3. The method according to claim 2, wherein the dispersant is at least one of polyacrylic acid, ammonium polymethacrylate and ammonium citrate, and the adding amount of the dispersant is lwt-20 wt% of the total mass of the carbon source, the phosphorus source and the heteroatom source.
4. The method of claim 2, wherein the reaction medium is at least one of ethylene glycol and isopropanol, and the amount of the reaction medium added is l00 wt-200 wt% of the total mass of the carbon source, the phosphorus source and the heteroatom source.
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| CN112018362B (en) * | 2020-08-31 | 2022-07-12 | 华中科技大学 | Phosphorus-carbon material and in-situ synthesis method and application thereof |
| CN113381014B (en) * | 2021-06-08 | 2023-03-03 | 西安亚弘泰新能源科技有限公司 | Preparation method of ultralow-temperature lithium ion battery negative electrode material |
| CN115528232B (en) * | 2022-10-08 | 2023-03-31 | 湖南钠能时代科技发展有限公司 | Preparation method of reed-derived hard carbon sodium electric anode material and energy storage battery |
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| CN101533900B (en) * | 2009-03-18 | 2012-05-16 | 清华大学 | Phosphorus composite material used for electrochemistry reversible lithium storage and preparation method thereof |
| CN105845906B (en) * | 2016-04-08 | 2018-11-23 | 清华大学 | Phosphorous anode material and preparation method thereof and lithium ion battery |
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