TWI378589B - Phosphorated composite, method for making the same, and battery using the same - Google Patents

Description

1378589 VI. Description of the Invention: [Technology Leading to the Invention] The present invention belongs to the field of electrochemical technology and relates to a composite material for electrochemical reversible lithium storage and a preparation method thereof. [Prior Art] [0002] Energy is closely related to the survival and development of human society. Since the beginning of the twentieth century, human society has entered a new era of rapid development, and various countries and regions in the world are undergoing rapid changes. At the same time, the overall trend of world energy consumption and social development and population growth have maintained positive growth. It is estimated that energy consumption will increase by 50% to 100% by 2020. However, fossil fuels (coal, oil, natural gas, etc.), which have long been the foundation of the global energy structure, have limited reserves, and fossil fuel combustion has caused serious pollution to the ecological environment and even endangered human survival. Therefore, various new energy sources such as solar energy, nuclear energy, wind energy, geothermal energy and ocean energy have attracted much attention because of the possibility of solving the above-mentioned resource and environmental problems. 'It is expected to play an increasingly important role in the sustainable development of the world economy. The conversion storage device, which is a chemical energy and an electric energy, can play an important role in various labor fields. At the same time, with the progress of society, people have a higher living environment. [Requirement, electric vehicles have a "zero emission," characteristics of the car development - an important direction, (four) also proposed for the battery The requirement of 4 is 1 high capacity 'smaller size, lighter weight and more usable life. Traditional secondary batteries, such as (4) battery batteries, nickel-cadmium batteries, etc. are difficult to reach ', ν η. • Female water', since the 199 heart (four) first (4) sub-battery has been industrialized" 098143813 [0003]

Form No. 0901 0982075043-0 1378589 Ion battery has become portable with high mass and volumetric capacity, high output voltage, low self-discharge rate, wide operating temperature range, fast charge and discharge and no memory effect. An ideal power source for electronic equipment and environmentally friendly electric vehicles. With the further popularization of portable electronic devices and the development of electric vehicles, lithium-ion batteries will occupy a broader market and gain a larger market share in the future. In order to meet the market demand for lithium-ion battery performance, the development of higher performance lithium-ion batteries has become a major goal in related research fields in the future.

[0004] The theoretical specific capacity of elemental phosphorus is 2594 mAh/g (mAh/g), while the theoretical specific capacity of graphite negative electrodes commonly used in commercial lithium ion batteries is 372 mAh/g, and more elemental tin is studied. The ritual ratio / Rong Dong is 992mAh / g, the theoretical specific capacity of the single stone eve is 42 (i 〇 inAh. / g. And one ' · \, / , ...... · ·-,. ' And the natural resources of alloys are limited, on the other hand, their prices are relatively high, so the development of new anode materials with abundant reserves and low cost is very theoretical and practical. V::

[0005] While an elemental phosphorus-based electron and an ion insulator, the reaction product may have a dissolution, an electrolytic conductivity i, and an electronically insulating reaction product in the electrolyte '..: ''乂'· wrapped on the surface of the living material to cause internal The active material fails, so it cannot be directly applied to the electrode active material. Hun-Joon Sohn et al. (Advanced materials, 2007, 19, 2465-2468) reported the application of elemental phosphorus to lithium-ion battery electrode materials to prepare harsh, expensive black phosphorus (a graphite-like elemental elemental phosphorus). The allotrope is an active material, which is composited with lead-graphite graphite to prepare a negative electrode material for lithium ion batteries, and the data of the article indicates that the electrode material prepared by the same process using red phosphorus as an active material does not have the availability 098143813 form No. A0101 Page 5 of 24 0982075043-0 1378589 SUMMARY OF THE INVENTION [0006] In view of the above, it is necessary to provide a phosphorus composite material for electrochemically reversible lithium storage and a preparation method thereof. [0007] A phosphorus composite material for electrochemically reversible lithium storage, comprising a conductive substrate and red phosphorus, the conductive substrate being at least one of a conductive carbon material and a conductive polymer, wherein the filled composite material is weighted by weight The content of the red filler is 15% to 90%, and the content of the conductive substrate is 10% to 85°/〇. [0008] A method for preparing a phosphorus composite material for electrochemically reversible lithium storage, comprising the steps of: mixing at least one of a conductive carbon material and an organic polymer as a raw material and red phosphorus to form a mixture, wherein the raw material The mass ratio of the red phosphorus to the red phosphorus is 0.1 to 5; the mixture is dried by heating under an inert atmosphere or under vacuum; and the dried mixture is placed in a reaction vessel, and heat treatment is performed under an inert atmosphere to gradually cool the red phosphorus after sublimation. The room temperature is from 250 ° C to 600 ° C to room temperature. Compared with the prior art, the phosphorus composite prepared by the invention can be used for electrochemical reversible lithium storage. In view of the mechanism of lithium ion battery, the reversible deintercalation of lithium into the electrode material, the phosphorus composite material of the invention can be used as two The electrode material of the secondary chemical power source, the battery with the phosphorus composite material as the active material can be reversibly charged and discharged in the temperature range of -20 to 80 °C. [Embodiment] Hereinafter, a phosphorus composite material for electrochemically reversible lithium storage of the present invention and a preparation method thereof will be described in detail with reference to the accompanying drawings. [0011] The present invention provides a phosphorus composite material for electrochemical reversible lithium storage, 0982075043-0

098143813 Form No. A0101 Page 6 of 24 13785.89 The phosphorus composite consists of two parts, one part is a conductive carbon material and/or a conductive polymer as a conductive matrix, and the other part is red phosphorus. In the material, the content of red phosphorus is 15% to 90% by weight, and the content of conductive carbon material and/or conductive polymer is 10% to 85%. [0012] The conductive substrate is at least one of a conductive carbon material and a conductive polymer. [0013] The conductive polymer is preferably a conjugated conductive polymer. The conductive polymer may be a product formed by the dehydrogenation carbonization reaction of the red phosphorus-catalyzed organic polymer. Further, the reaction for forming the conductive polymer may be a dehydration, degassing hydrogenation or deamination reaction of the organic polymer. [0014] The organic polymer may be selected from polypropylene, / polyacrylonitrile, polystyrene / ' ', polyethylene oxide, polyvinyl alcohol, polydioxane 4, polyvinylidene fluoride, polyethylene One or more of polyvinyl fluoride, poly 1,2-dichloroethylene, polytetrafluoroethylene, polymethyl methacrylate and phenolic resin. It is to be understood that the organic polymer is not limited to the above-exemplified substances as long as it can form a conjugated conductive material: organic polymers are all within the scope of the present invention. y ' '' [0015] The conductive carbon material may be selected from one or more of activated carbon, acetylene black, conductive graphite, and conductive amorphous carbon (amorphous carbon). [0016] The amorphous carbon may be formed by dehydrogenation of an organic substance such as hydrazine or cellulose, thereby making the amorphous carbon conductive. [0017] The present invention provides a method for preparing a phosphorus composite material for electrochemically reversible lithium storage, comprising the following steps: [0018] Step one, at least one of a conductive carbon material and an organic polymer is used as the original form of 0982075043-0 098143813 No. A0101 Page 7 of 24 1378589 The material and the red phosphorus are uniformly mixed, wherein the mass ratio of the raw material to the red phosphorus is about 0.1 to 5 (that is, the quality of the raw material: the quality of the red phosphorus is 1: 10 to 5) [0019] Step 2, heating the above mixture under an inert atmosphere or under vacuum: and [0020] Step 3, placing the dried mixture into the reaction dad, heat treatment under an inert atmosphere to make the red phosphorus sublimate The temperature is gradually cooled to room temperature, and the heat treatment temperature is from 250 ° C to 600 ° C.

[0021] Specifically, in the above step 1, the conductive carbon material and/or the organic polymer and the red phosphorus may be uniformly mixed by grinding or ball milling. / [ ' [0022] The organic polymer may be selected from the group consisting of polypropylene, polyacrylonitrile, polystyrene, polyethylene oxide, polyvinyl alcohol, polyvinylidene gas, polyvinylidene fluoride, polyvinyl chloride, poly One or more of vinyl fluoride, poly 1,2-diethylene, polytetrafluoroethylene, polymethyl methacrylate and phenolic resin. The organic polymer can be heated to the above temperature and promoted in red phosphorus

A conductive polymer is formed under the action and is compounded in situ with the red phosphorus. Yes, /' It is understood that all organic polymers which can be formed by heating and catalyzing the red phosphorus are within the scope of the present invention. The organic polymer may also be selected from one or more of cellulose and a saccharide such as glucose or polysaccharide. By heating to the above temperature, a dehydrogenation reaction occurs to form conductive amorphous carbon, and the amorphous carbon and the red phosphorus are compounded in situ. [0024] The conductive carbon material may be selected from the group consisting of activated carbon, acetylene black, conductive graphite, and conductive One or more of the amorphous carbons. 098143813 Form No. A0101 Page 8 of 24 0982075043-0 1378589 [0025] The conductive carbon material or organic polymer is in the form of a powder, a chip, a granule or a fiber. In the second step, the inert atmosphere may be a dry high purity argon gas or a dry high purity nitrogen atmosphere. The drying temperature may be selected from 50 ° C to 120 ° C, and the drying time may be selected from 1 hour to 10 hours to evaporate a small amount of water and impurities in the mixture. [0027] In the third step, the heat treatment time in an inert atmosphere may be selected from 1 hour to 48 hours, depending on the amount of the reactant. The heat-treated reaction product is cooled to room temperature with the reaction vessel to obtain a conductive polymer formed of an organic polymer or a conductive carbon material as a conductive matrix, and an electrochemically reversible lithium hydride formed by in-situ recombination with sublimated red phosphorus by adsorption. Phosphorus composite • ' ' / material. [0028] It can be understood that the phosphorus composite material can be used for electrochemically reversible lithium storage, for example, as an electrode active material in a lithium ion battery. The lithium ion battery includes a positive electrode, a negative electrode, and an electrolysis; and the negative electrode is made of the above-mentioned phosphorus composite material. The positive electrode 7: method can also be a commonly used positive electrode active material, such as at least one of an acid chain, an acid acid, and an acid chain. The electrolyte may include an electrolyte salt and a solvent for dissolving the electrolyte salt, and the electrolyte salt may be lithium hexafluorophosphate, and the solvent may be decene carbonate, ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, At least one of dipropyl carbonate and cesium carbonate. Embodiment 1 [0030] A method for preparing a phosphorus composite material for electrochemically reversible lithium storage, the 0982075043-0 098143813 Form No. A0101 Page 9 of 24 1378589 The method steps are as follows: [0031] Step 1 Polyacrylonitrile (PAN, product of Aldrich, in the form of small particles) and red phosphorus (purity of red phosphorus higher than industrial purity) are uniformly mixed by grinding, wherein the mass ratio of polyacrylonitrile to red filling is 1:4. [0032] Step 2, drying the mixture under heating in a high-purity nitrogen atmosphere, the drying temperature is 70 ° C, and the drying time is 6 hours; [0033] Step 3, the dried mixture is placed in a tube furnace, In a dry high-purity nitrogen atmosphere, heat treatment is carried out to sublimate red phosphorus, the reaction temperature is 500 ° C, the reaction time is 12 hours, and the furnace is cooled to room temperature. During the heat treatment, red phosphorus catalyzed dehydrogenation of polyacrylonitrile After the carbonization reaction, a conjugated conductive polymer is formed, and red phosphorus forms a phosphorus composite with the conductive polymer through sublimation-adsorption. [0034] The obtained phosphorus composite material is composed of two parts, one is a conductive polymer as a conductive matrix (the red phosphorus-catalyzed polyacrylonitrile dehydrocarbonization reaction, - '· /, - product), and the other part is red In the phosphorus and phosphorus composite materials, the red filler content is 55% by weight (where the scale content is determined by an elemental analyzer), and the conductive polymer content is 45%. [0035] The phosphorus composite material prepared in Example 1 was tested for charge and discharge performance as an active material of a lithium ion battery, specifically using polytetrafluoroethylene as a binder, acetylene black and conductive graphite as a conductive agent (including acetylene black and conductive graphite) The mass ratio is 1:1), and ethanol is used as a dispersant (wherein various materials are phosphorus composite materials by mass ratio: binder: conductive agent: dispersant = 8 : 10 : 5 : 5), and foamed nickel is used as a current collector. The electrode was prepared by the above materials, and dried under vacuum at 120 ° C for 24 hours, using a lithium metal plate as a counter electrode, using 098143813 Form No. A0101 Page 10 / Total 24 page 0982075043-0 1378589 lmol / L of hexafluoroacid a mixed solution of a chain (LiPFe) in ethylene carbonate vinegar, diethyl bromide and dinonyl carbonate, wherein a volume ratio of ethylene carbonate, diethyl carbonate and dinonyl carbonate is 1: 1: The diaphragm is made of celgard 2400 to form a battery. The battery open circuit voltage is about 2. 7V, the initial discharge specific capacity exceeds 650mAh/g, and the capacity still exceeds 400mAh/g after 40 cycles. [0036] Example 2 [0037] A method for preparing a phosphorus composite material for electrochemically reversible lithium storage, the method steps are as follows: [0038] Step one, polyethylene terephthalate (PVDC, Aldrich product, morphology) For the powder) and red phosphorus (the purity of red phosphorus is higher than the purity of the work 通过 by grinding - / to make the mixture uniform, wherein the ratio of polyethylene to red phosphorus / mass ratio is 1: 2; [0039] Step two, in Drying the mixture under high-purity nitrogen atmosphere, drying at 80 ° C, drying time I; V, [0040] Step 3, mixing after drying into a tube furnace, in a high-purity nitrogen atmosphere Under the heat treatment, the red phosphorus is sublimated, the reaction temperature is 450 ° C, the reaction time is 3 hours, and the furnace is cooled to room temperature. During the heat treatment, red phosphorus catalyzes the dehydrogenation and carbonization reaction of the polyvinylidene chloride. Co-type conductive polymer, while red phosphorus forms a phosphorus composite with conductive polymer through sublimation-adsorption. [0041] The obtained phosphorus composite consists of two parts, a conductive polymer as a conductive matrix (red phosphorus catalysis) Polyposition The product of dehydrogenation and carbonation of vinyl chloride), the other part is red phosphorus as lithium storage material, phosphorus composite 098143813 Form No. A0101 Page 11 / 24 pages 0982075043-0 1378589 In the material, by weight, red The filling content is 40% (wherein the lin content is determined by an elemental analyzer), and the conductive polymer content is 60%. [0042] The phosphorus composite material prepared in Example 2 is charged and discharged as an active material of a lithium ion battery. Performance test, specifically using polytetrafluoroethylene as a binder, acetylene black and conductive graphite as a conductive agent (wherein the mass ratio of acetylene black and conductive graphite is 1:1), ethanol as a dispersant, and foamed nickel as a current collector to prepare an electrode. Among them, various substances are phosphorus composite materials according to mass ratio: binder: conductive agent: dispersant=8 ·· 10 : 5 : 5, using lithium metal as the counter electrode, using 1 mol/L of LiPFe in ethylene carbonate, carbonic acid a mixed solution of ethyl ester and dimethyl carbonate, wherein the volume ratio of ethylene carbonate, diethyl carbonate and dinonyl carbonate is 1: 1: 1, and the separator is made of celgard 2400 to form a battery. The voltage is about 2. 7V, the initial discharge specific capacity exceeds 1150mAh/g, and the capacity still exceeds 300mAh/g after 40 cycles. [0043] Embodiment 3 [0044] A phosphorus composite material for electrochemical reversible lithium storage The preparation method, the method steps are as follows, [0045] Step one, the activated carbon (morphological powder) and red phosphorus (red phosphorus purity higher than industrial purity) are uniformly mixed by ball milling, wherein the mass ratio of activated carbon to red phosphorus is 1 [0046] Step 2, in a dry high-purity nitrogen atmosphere, the above mixture is dried by heating, the drying temperature is 100 ° C, and the drying time is 6 hours;

[0047] Step 3, the dried mixture is placed in a reaction kettle, and subjected to heat treatment in a dry high-purity nitrogen atmosphere to sublimate red phosphorus, and the reaction temperature is 470 ° C. 098143813 Form No. A0101 Page 12 / Total 24 pages 0992075043 -0 [0048] 1378589 [0049]

[0051] 098143813, the reaction time is 6 hours, the furnace is cooled to room temperature, and the activated carbon adsorbs the sublimated phosphorus vapor during the heat treatment to obtain an electrochemical reversible storage composite material with activated carbon as a conductive matrix. . The obtained phosphorus composite material is composed of two parts, one is a carbon material (activated carbon) as a conductive matrix, and the other part is red phosphorus. In the phosphorus composite material, the content of red content is 30% by weight (filled here) The content is determined by an elemental analyzer and the activated carbon content is 70%. The phosphorus composite prepared in Example 3 was tested for charge and discharge performance as an active material of a lithium ion battery, specifically using a polyvinylidene fluoride-hexafluoropropylene copolymer as a binder, acetylene black as a conductive agent, and N-mercapto beer. The alkane is used as a powder-dispersant, and the copper foil is used as a current collector to form an electrode, wherein each bismuth substance is of a mass ratio, and the ratio is a phosphorus composite material: a binder: a conductive agent=4:, 5: .5/, a metal Lithium as a counter electrode, using 1 mol/L of LiPFe in ethylene carbonate, carbonic acid

A mixed solution of D ethyl ester and dinonyl carbonate, wherein a volume ratio of ethylene carbonate, diethyl carbonate and dimethyl carbonate is 1:1: 1, and the separator is composed of ce 1 gard 2400. Please refer to FIG. 1 for a typical charging and discharging operation of the phosphorus composite material prepared by the present embodiment as #I: cell electrode material.

X > X electric curve. The abscissa indicates the battery charge and discharge capacity (mAh/g), and the ordinate indicates the battery voltage (V). This figure shows that the phosphor composite has a more pronounced charge and discharge platform. The battery open circuit voltage is about 2. 6V, the initial discharge specific capacity exceeds 900mAh/g, and the capacity still exceeds 500mAh/g after 40 cycles. Embodiment 4 A method for preparing a phosphorus composite material for electrochemically reversible lithium storage, the method steps are as follows, Form No. A0101, Page 13 of 24, 0982075043-0 1378589 [0052] Step one, conductive graphite (formation is The powder and the red phosphorus (the purity of the red phosphorus is higher than the industrial purity) are uniformly mixed by ball milling, wherein the mass ratio of the conductive graphite to the red scale is 1:1; [0053] Step 2, in a dry high-purity argon atmosphere, The mixture is dried by heating, the drying temperature is 100 ° C, and the drying time is 6 hours; [0054] Step 3, the dried mixture is placed in the reaction dad, and heat-treated under a dry high-purity argon atmosphere to sublimate the red phosphorus. The reaction temperature is 600 ° C, the reaction time is 6 hours, and the furnace is cooled to room temperature, and the conductive graphite adsorbs the sublimated phosphorus vapor during the heat treatment to obtain an electrochemical reversible lithium storage phosphorus composite material with conductive graphite as a conductive matrix. . [0055] The obtained phosphorus composite material is composed of two parts, one is a carbon material (conductive graphite) as a conductive matrix, and the other part is red phosphorus, and the phosphorus composite material has a red filling content of 15% by weight. Here, the content is determined by an elemental analyzer, and the conductive matrix content is 85%. [0056] The phosphorus composite material prepared in Example 4 was tested for charge and discharge performance as an active material of a lithium ion battery, specifically using a polyvinylidene fluoride-hexafluoropropylene copolymer as a binder, and acetylene black as a conductive agent, Ν-曱The pyrrolidone is used as a dispersing agent, and the copper foil is used as a current collector. Among them, various materials are phosphorus composite materials by mass ratio: binder: conductive agent=4:5:5, metal lithium is used as the counter electrode, and lmol/L LiPFe is used. a mixed solution of ethylene carbonate, diethyl carbonate and carbonic acid dinonyl ester, wherein the volume ratio of ethylene carbonate, diethyl carbonate and dimethyl carbonate is 1: 1: 1, and the separator is celgard 2 4 0 0, constitute the battery. [0057] The phosphorus composite material prepared in Example 4 and the lithium metal sheet constitute a half-cell charge and discharge 098143813 Form No. A0101 Page 14 of 24 1378589 The electric curve and cycle performance are shown in FIG. 2 and FIG. Fig. 2 shows a typical charge and discharge curve when the red disc/conductive graphite composite material equipped with this embodiment is used as a battery electrode material. The abscissa indicates the battery charge and discharge capacity (Μ"), and the ordinate indicates the battery voltage (v). The figure shows that the phosphorus composite material has a more obvious charge and discharge platform. Fig. 3 shows a typical battery cycle performance curve of the red phosphorus/conductive graphite composite material prepared by the present embodiment as a lithium battery electrode material. The abscissa indicates the number of charge and discharge cycles of the battery, and the ordinate is the specific capacity (mAh/g). The initial discharge specific capacity exceeds 9〇〇mAh/g. After 60 charge and discharge cycles, the capacity is still higher than 50〇mAh/g, and the charge and discharge efficiency is close to 100%. [0058] It can be understood that the conductive polymer and/or conductive carbon material can be formed in a manner that is directly combined with the red phosphorus in situ after forming the conductive polymer or the conductive carbon material in situ. The conductive polymer and/or conductive carbon material is mixed with red phosphorus to prepare the phosphorus composite. [0059] In summary, the present invention has indeed met the requirements of the invention patent, and the patent application is filed according to law. However, the above-mentioned ones only have a preferred embodiment of +fare, which cannot limit the scope of the patent in this case. Equivalent modifications or variations of the person skilled in the art of the present invention in the spirit of the present invention are intended to be included in the scope of the following claims. BRIEF DESCRIPTION OF THE DRAWINGS [0060] FIG. 1 is a charge and discharge curve of a half-cell composed of a phosphorus composite material prepared in Example 3 and a lithium metal sheet. 2 is a charge and discharge curve of a half-cell composed of a phosphorus composite material prepared in Example 4 and a lithium metal sheet. 098143813 Form No. A0101 Page 15 of 24 0982075043-0 1378589 [0062] FIG. 3 is a graph showing the charge-discharge cycle performance of the phosphorus composite material prepared in Example 4 and the lithium metal sheet-constituting half-cell. [Main component symbol description] [0063] None 098143813 Form No. A0101 Page 16 of 24 0982075043-0

Claims (1)

1378589 VII. Patent application scope: 1. A phosphorus composite material for electrochemical reversible lithium storage, wherein the composite material is composed of a conductive substrate and a red filler. The conductive matrix material is a conductive carbon material and conductive. At least one of the polymers, wherein the content of the red phosphorus is 15% to 90% by weight, and the content of the conductive substrate is 10% to 85°/〇. 2. The phosphorus composite material for electrochemically reversible lithium storage according to claim 1, wherein the conductive polymer is a conjugated conductive polymer. 3. The phosphorus complex for electrochemical reversible lithium storage as described in claim 1 The composite material, wherein the conductive polymer is a product of dehydrogenation carbonization reaction, dehydration reaction, dechlorination, hydrogen anti-horse or deamination reaction of a red phosphorus-catalyzed organic polymer. / '' y' 4 . Phosphorus complex for electrochemical reversible lithium storage as described in claim 3 The invention relates to a composite material, wherein the organic polymer is polypropylene, polyacrylonitrile, polystyrene, polyethylene oxide, polyvinyl alcohol, polyvinylidene gas, polyvinylidene fluoride, polyvinyl chloride, polyfluoride Ethylene, poly 1, diethylene, poly(difluoroethylene), polymethacrylic acid: one of phenolic resin or V-. 'V./ several. 5. The phosphorus composite material for electrochemically reversible lithium storage according to claim 1, wherein the conductive carbon material is one or more of activated carbon, acetylene black, conductive graphite, and conductive amorphous carbon. Kind. 6. The phosphorus composite material for electrochemically reversible lithium storage according to claim 5, wherein the conductive amorphous carbon is formed by dehydrogenation of a saccharide or cellulose. 7. A composite material for electrochemically reversible lithium storage according to the application and scope of claim 1, 098143813, Form No. A0101, page 17 of 24, 0982075043-0 1378589, wherein the conductive substrate is pyrolyzed The polyacrylonitrile content was 45%; the red dish content was 55%. 8. The phosphorus composite material for electrochemically reversible lithium storage according to claim 1, wherein the conductive substrate is pyrolytic polystyrene, the content is 60%; and the red phosphorus content It is 40%. 9. The phosphorus composite material for electrochemically reversible lithium storage according to claim 1, wherein the conductive substrate is activated carbon in an amount of 70%; and the red phosphorus content is 30%. 1. The phosphorus composite material for electrochemically reversible lithium storage according to claim 1, wherein the conductive substrate is conductive graphite in an amount of 85%; and the red end content is 15%. . 11. A method for preparing a phosphorus composite material for electrochemically reversible lithium storage, comprising the steps of: mixing at least one of a conductive carbon material and an organic polymer as a raw material with red phosphorus to form a mixture, wherein the raw material is red The mass ratio of phosphorus is 0.1 to 5; the mixture is dried by heating under an inert atmosphere or under vacuum; and /. The dried mixture is placed in a reaction vessel, and heat treatment is carried out under an inert atmosphere to gradually cool the red phosphorus after sublimation. The method for preparing a phosphorus composite material for electrochemically reversible lithium storage according to claim 11, wherein the raw material and the heat treatment temperature are from 250 〇C to 600 〇C 〇12. The red phosphorus is uniformly mixed by grinding or ball milling. The method for producing a phosphorus composite material for electrochemically reversible lithium storage according to claim 11, wherein the organic polymer forms a conductive polymer by the heat treatment step. 098143813 Form No. A0101 Page 18 of 24 0982075043-0 1378589 14. The method for preparing a phosphorus composite material for electrochemically reversible lithium storage according to claim 13, wherein the organic polymer is polypropylene, polyacrylonitrile, polystyrene, polyethylene oxide, Polyvinyl alcohol, polyvinylidene gas, polyvinylidene fluoride, polyethylene, polyvinyl fluoride, poly 1,2-diethylene, polytetrafluoroethylene, polymethyl methacrylate and phenolic One or several of the resins. The method for producing a phosphorus composite material for electrochemically reversible lithium storage according to claim 11, wherein the organic polymer undergoes a dehydrogenation reaction to form a conductive amorphous by the heat treatment step. carbon. The method for producing a phosphorus composite material for electrochemically reversible lithium storage according to claim 15, wherein the organic polymer is cellulose and sugar: ^, class. The method for producing a phosphorus composite material for electrochemically reversible lithium storage according to claim 15, wherein the saccharide is one or more of glucose or polysaccharide. 18. A phosphorus complex for electrochemically reversible lithium storage as claimed in claim 11 19.20. The method for preparing a composite material, wherein the conductive carbon material is one or more of activated carbon, acetylene black, conductive graphite, and conductive amorphous. The method for preparing a phosphorus composite material for electrochemically reversible lithium storage according to claim 11, wherein the inert atmosphere is a dry high purity argon gas or a dry high purity nitrogen atmosphere, and the drying temperature is 50. °C~120 ° C, drying time is 1 hour ~ 10 hours. The method for producing a phosphorus composite material for electrochemically reversible lithium storage according to claim 11, wherein the heat treatment time in an inert atmosphere is from 1 hour to 48 hours. Phosphorus complex for electrochemically reversible lithium storage as described in claim 11 of the patent application No. 119143813, Form No. A0101, page 19, page 24, 0982075043-0 1378589, a method for preparing a composite material, wherein the form of the raw material is powder The method for preparing a phosphorus composite material for electrochemically reversible lithium storage according to claim 11, wherein the raw material is polyacrylonitrile, the polyacrylonitrile and the red The mass ratio of phosphorus was 1:4, and the heat treatment temperature was 500 °C. The method for preparing a phosphorus composite material for electrochemical reversible lithium storage according to claim 11, wherein the raw material is polyvinylidene gas, the quality of the polyethylene dioxide and the red phosphorus The ratio is 1:2, and the heat treatment temperature is 450t. The method for preparing a phosphorus composite material for electrochemically reversible lithium storage according to claim 11, wherein the raw material is activated carbon, and the mass ratio of the activated carbon to the red phosphorus is 1:1. The heat treatment temperature was 470 °C. The method for preparing a phosphorus composite material for electrochemically reversible lithium storage according to claim 11, wherein the raw material is conductive graphite, and the mass ratio of the conductive graphite to red phosphorus is 1:1. The heat treatment temperature was 600 °C. 26. A battery using a phosphorus composite material as an electrode active material, comprising: a positive electrode, a negative electrode, and an electrolyte, wherein the active material of the negative electrode is used in any one of items 1 to 1 of the patent application scope. The phosphorus composite material. 27. The battery using the phosphorus composite material as the electrode active material according to claim 26, wherein the active material of the positive electrode is at least one of acid recording, acid recording, lithium manganate, and lithium iron phosphate. . The battery using the phosphorus composite material as the electrode active material according to claim 26, wherein the electrolyte solution comprises an electrolyte salt and a solvent for dissolving the electrolyte salt, the electrolyte salt being lithium hexafluorophosphate, the solvent being carbonic acid Terpene ester, ethylene carbonate, propylene carbonate, dinonyl carbonate, carbonic acid No. 098143813 Form No. A0101 Page 20 of 24 0982075043-0 1378589 Ethyl ester, dipropyl carbonate and ethyl carbonate One. 098143813 Form No. A0101 Page 21 of 24 0982075043-0