TW201123593A - Organic phosphorated polymer, method for making the same, and lithium battery using the same - Google Patents

Abstract

The invention relates to an organic phosphorated polymer and a method for making the same. The main structure of the organic phosphorated polymer is a conductive polymer. In the conductive polymer, phosphor has a weight ratio of 10% to 85%. The organic phosphorated polymer has a property of electrochemical rechargeable lithium storage and can be used for an active material in a lithium battery.

Description

201123593 VI. Description of the Invention: [Technical Field] The present invention relates to the field of electrochemical technology, and in particular to an organic phosphating polymer for electrochemically 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. Every country and region in the world is 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 by 2020, Leyuan consumption will increase by 5arl〇〇p but for a long time as the basis of global energy structure: fossil fuel, material (. coal, oil and natural gas, etc.) reserves are limited, and fossil fuel combustion: burning caused by the ecological environment Serious pollution 'even threatens human survival. Therefore, solar energy, such as nuclear energy, wind energy, geothermal energy and ocean energy, have attracted much attention because of the potential to solve these resource and environmental problems, and are expected to play an increasingly important role in the sustainable development of the world economy. As a chemical conversion and storage device for chemical energy, chemical power can play an important role in various renewal areas. [0003] At the same time, with the advancement of society, people have higher requirements for the living environment. Electric vehicles have zero The characteristics of emissions have become an important direction for the development of automobiles in the future, but at the same time, higher requirements have been placed on batteries: higher capacity, smaller size, lighter weight and longer service life. Secondary batteries, such as lead-acid batteries, nickel-hydrogen batteries, and recording batteries, are difficult to meet these requirements. However, since the Japanese company Sony first took the lead in industrializing lithium-ion batteries in 1999, lithium 098143825 Form No. A0101 Page 3 / Page 24 0982075059-0 201123593 Ion battery with its mass and volumetric capacity, high round out The voltage, low self-discharge rate, wide operating temperature range, fast charge and discharge, and no memory effect have become ideal power sources for portable electronic devices and environmentally friendly electric vehicles. With the further popularization of portable electronic devices and the development of electric eight-cars, lithium-ion batteries will occupy a broader market in the future and gain a larger market share. 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] [0005] The theoretical specific capacity of elemental phosphorus is 2594 mAh/g (mAh/g), and the theoretical specific capacity of inorganic packing exceeds mAh/g. At present, the theoretical specific capacity of the graphite negative electrode commonly used in commercial ion batteries is 37. The theoretical specific capacity of the elemental tin with more research is 992aAh/g, and the theoretical specific capacity of the elemental stone is 42〇〇mAh/ g. Due to the limited natural resources of metals and alloys and their relatively high prices, it is of theoretical and practical significance to develop new disk-based anode materials with abundant reserves and low cost. However, the application of single-disc discs to reversible lithium storage materials is fresh. It has been reported that at present, only the report of the single M is based on the electric _ τ inverse gamma (four) Hi J〇〇n Sohn et al. (Advanced materials, 2〇〇7, 19, 2465-2468) 'the preparation conditions are harsh, the price The expensive black phosphorus (the allotrope of elemental phosphorus of a kind of graphite structure) is an active material, which is compounded with conductive graphite to prepare a negative electrode material for a clock ion battery, and the inexpensive red fill 'even if it is compounded by the same process, It is still not available. For phosphides, the phosphides with electrochemically reversible lithium storage are mostly inorganic phosphides such as LiMP (M=Ti, V, etc.), MnP4, CoP3, CuP2, Cu3P, Fe. ~, Li2CuP, TiP2# 098143825 Form No. A0101 Page 4 / 24 pages 0982075059-0 201123593. However, the cycling performance of these phosphides is generally poor. [0006] Elemental phosphorus and inorganic phosphides are used in electrochemical reversible lithium storage materials. Its inherent disadvantages. For elemental phosphorus, in addition to the price of black phosphorus, low-cost, lithium-rich red phosphorus and white phosphorus are electron and ion insulators, so it can not be directly applied to electrochemical storage materials, even if used The proportion of conductive materials that must be added to a large amount of electrons and ionic conductors may be as high as 50% by weight, so that the energy density of the electrodes and even the battery is greatly reduced. For inorganic phosphides, if the lithium storage reaction is thoroughly carried out, electrochemical reversibility is formed. Poor Li, resulting in large first irreversible capacity and poor cycle performance from rain. Most of the inorganic phosphide preparation conditions are complicated, and the preparation process is uneconomical. [Summary of the Invention] [0007] In view of this, Electrochemically active phosphorus-containing materials are necessary. [00〇8] - Organic phosphorus phosphating for electrochemical reversible lithium storage The organic phosphating polymer is composed of two parts: one part is a conductive polymer primary bond; the other part is connected to the conductive polymer main chain and has an electrochemical property. An active multi-disc group Pm side chain, and a functional group ri*R2 side bond, the organophosphorus polymer structural unit is:

One or more of the polyphosphorus groups, p and p are covalently bonded, 111 is an integer from 1 to 12; ri and R2 are methyl, methoxymethyl, and two gas 098143825 Form No. A0101 Page 5 / total 24 yellow 0992075059-0 201123593 One or more of a group, a difluoroindenyl group, a fluoromethyl group, an ether group, a fluorine group, a chlorine group, a cyano group, a phenyl group, an amino group and a hydrogen group. [0010] An organophosphorus polymer for electrochemically reversible lithium storage, wherein the organic phosphating polymer is a polymer conductive polymer, the organic phosphating polymer consists of two parts: a part is a conductive polymer main a chain; another portion is a polyphosphorous group Pm side chain which is linked to the conductive polymer backbone and has an electrochemically active polyphosphorus group, and the organophosphorus polymer structural unit is

Pm Pm Pstn is linked by a covalent bond, and m is an integer of 1 to 12. [0011] A lithium ion battery, wherein the active material of the battery comprises at least one of the above-described organic phosphating polymers. [0012] A method for preparing an organophosphorus polymer for electrochemically reversible lithium storage, comprising the steps of: (1) uniformly mixing an organic polymer with elemental phosphorus to form a mixture, wherein the organic polymer in the mixture The mass ratio to the elemental phosphorus is 0. b; (2) heating the mixture under an inert atmosphere or under vacuum; (3) placing the dried product in a closed reaction vessel, filling with an inert gas, and performing heat treatment , the reaction temperature is 25 (TC ~ 600 ° C, the reaction time is 1 hour ~ 48 hours, elemental phosphorus gasification, organic polymer dehydrogenation phosphating reaction, with the furnace cooled to room temperature to obtain a product; (4) will The heat-treated product is immersed in an alkaline solution; (5) the product is treated with an acidic solution, 098143825, Form No. A0101, page 6 / page 24, 0982075059-0, 201123593, to neutralize the alkaline solution; and (6) The product is washed with ionic water until the washed deionized water is neutral, and the washed product is dried to obtain an organic phosphatized polymer. [0013] Compared with the prior art, phosphorus and polyphosphorus groups are grafted. To the conductive polymer The utility model can avoid the disadvantage that the elemental phosphorus is not electrically conductive, and can avoid the disadvantage of poor reversibility of the inorganic phosphide reaction. The organic phosphating polymer prepared by the invention can be used as an electrode material of a secondary chemical power source, and the battery with the material as the active material can be used. Reversible charge and discharge at room temperature, because the PP bond is completely broken during the charge and discharge cycle, the reversibility of lithium storage of the material is better. The polymer of this structure acts as a lithium storage active material, electrochemical The active phosphorus functional group or polyphosphorus group is immobilized on the conductive polymer backbone to avoid dissolution of phosphorus or phosphide during deintercalation of lithium. [0014] The organophosphorus polymer prepared by the present invention is environmentally friendly, not contain,

The capacity of heavy metals such as Ni after 10 cycles is still higher than 5 〇〇 mAh/g. [Embodiment] [0015] The present invention provides a step-by-step description of the present invention in conjunction with the accompanying drawings. [0016] The present invention provides an organophosphorus polymer for electrochemically reversible lithium storage, wherein 'the organic phosphatized polymer is a conductive polymer, wherein the organic phosphating polymer is dehydrogenated and deuterated to obtain a cerium [0017] wherein the organic phosphating polymer has a weight fraction of phosphorus of 1% to 85%. The electrochemical specific capacity is from 250 mAh/g to l500 mAh/g. .

[0018] The present invention further provides a method for preparing an organically filled polymer for an electrochemical reversible storage battery, the method comprising the following steps: 098143825 Form No. A0101 Page 7 / Total 24 Page 0992007559-0 201123593 [0019] 1) uniformly mixing the organic polymer and the elemental phosphorus to form a mixture, wherein the mass ratio of the organic polymer to the elemental phosphorus in the mixture is 0. 4; [0020] (2) under an inert atmosphere or under vacuum, Heating and drying the mixture of the step (1); [0021] (3) The mixture dried by the step (2) is placed in a closed reaction vessel, filled with an inert gas, and heat-treated at a temperature of 250 ° C to 600 ° C, gasifying the elemental phosphorus, and dehydrogenating the organic polymer to obtain a heat-treated product and cooling to room temperature with the reaction vessel; [0022] (4) using the heat-treated product to be alkaline The solution is soaked to remove residual phosphorus; and [0023] (5) The product after the alkaline solution is soaked in step (4) is adjusted to neutrality and dried. [0024] The organic polymer is polyethylene, poly 1,2-diethylene, polyvinylidene chloride, polychloroethylene, polytetrafluoroethylene, polyvinylidene fluoride, polyvinylidene fluoride One or more of polystyrene, polyoxyethylene, polyacrylonitrile, and polymethyl methacrylate. It is to be understood that the organic polymer is not limited to the above-listed substances, and other organic polymers which can be dehydrogenated and phosphatized with elemental phosphorus are within the scope of the present invention. [0025] The organic polymer form may be a powder, a small piece, a particle or a fiber, so that the dehydrogenation phosphating reaction can be sufficiently carried out. For example, the organic polymer can be a nanopowder. The elemental phosphorus is preferably red phosphorus, and may additionally be white phosphorus or black phosphorus. [0027] The method of mixing the step (1) is grinding, ball milling or the organic poly 098143825 form number A0101 page 8 / total 24 page 0992007559-0 201123593 [0028] [0029] [0030] Ο [0031] ] Q [0032] The compound is dissolved in a solvent to be a solution and mixed with the elemental phosphor powder. The solvent is selected from the group consisting of acetonitrile, acetone, N,N-dimethyldecylamine, and N-methylindole. One or more of verbaneous, water or ethanol. The inert gas of the step (2) is nitrogen or a rare gas such as argon, and the drying degree is 50 C~12 (TC, drying time is 8 hours to 48 hours. The heat treatment time of the step (3) is regarded as the mixture. Depending on the amount, it may be 1 hour to 48 hours. The linger solution of the step (4) may be one or more of ammonia water, aqueous sodium hydroxide solution and aqueous potassium hydroxide solution. Specifically, it may be: the product after being soaked with the empirical solution in the acidic solution neutralization step; and the product is washed with deionized water until the deionized water after the strip is neutral, and the washed product is at 50X: 〜l〇 ( Drying at rc temperature, drying time is 6 hours to 48 hours. The acidic solution may be a nitrogen acid aqueous solution, an aqueous hydrochloric acid solution, and a sulfuric acid water-soluble one or a mixture of sulphuric acid. It is understood that the organic phosphating polymer can be used for Electrochemical reversible lithium storage, for example, as an electrode active material used in a lithium ion battery. The lithium ion battery includes a positive electrode, a negative electrode and an electrolyte, and the active material of the negative electrode is used to employ the above organic phosphating polymer. The polar active material may be a conventional positive electrode active material such as at least one of lithium cobaltate, lithium nickelate, lithium manganate, and iron phosphate. The electrolyte may include an electrolyte salt and a solvent for dissolving the electrolyte salt. The electrolyte salt may be hexafluorophosphoric acid, and the cereal agent may be a methyl vinegar carbonate, a sulphuric acid sulphur, an acrylonitrile sulphide, an acid s-S|, a diacetic acid carbonate, a propylene carbonate And at least one of the esters of Form A No. 098143825 Form No. A0101 Page 9 of 24 0982075059-0 201123593 [0034] [0039] [0039] Example 1 The method for preparing an organically filled polymer for electrochemical reversible manure comprises the following steps: (1) mixing polyacrylonitrile with an elemental hydrazine to obtain a mixture, and in this embodiment, the method of the combination is The polyacrylonitrile is mixed with the _ powder by dissolving N,N_-dimethyl ketoamine into a solution, and the mass ratio of the poly(10) nitrile to the red dish is 〇·25, and the form of the polyacrylonitrile is granules. Weight average molecular weight (Mw) = 86200, number average molecular weight (Mn) = 226 〇〇 The single-disc plate is a red dish with higher purity than industrial purity; (2) The mixture in the above step is heated and dried under a dry nitrogen atmosphere at a drying temperature of 60 ° C and a drying time of 8 hours; (3) placing the dried mixture In the closed reaction dad, filled with inert gas nitrogen, heat treatment, heat treatment capacity is 450, heat treatment time 12 hours 'in the heat treatment process, bismuth phosphorus gasification, the polyacrylonitrile dehydrogenation phosphating reaction' The heat-treated product is cooled to room temperature with the reaction vessel, (4) the heat-treated product is immersed in an aqueous solution of sodium hydroxide to remove residual phosphorus; and (5) the product of the step (4) is neutralized with an aqueous hydrochloric acid solution and deionized. The water-washed product was neutralized to the deionized water after washing, and the washed product was dried at a temperature of 60 C for a drying time of 14 hours to obtain the organic phosphatized polymer. 098143825 Form No. A0101 Page 10 / Total 24 Page 0992007559-0 201123593 [0040] The obtained organic phosphating polymer is a polymer conductive polymer, and the organic phosphating polymer is composed of two parts: a part is a conductive polymer main chain; The other part is an electrochemically active polyphosphorus group Pm side chain, the organic phosphating

During the cleavage dehydrogenation of the ruthenium, P participates in the cyclization or dehydrogenation of the polymer to form a phosphorus-containing functional group, wherein Pm represents an integer of the polyphosphorus group * m being a group of 12, and in the polyphosphorus group Pm, P and P are covalently bonded, and the formed Pm connects two or more conductive polymer backbones. The degree of polymerization of the organophosphorus polymer is less than or equal to the degree of polymerization of the polymer precursor (polyacrylonitrile). The phosphorus content of the organophosphorus polymer is about 56% by weight (determined by elemental analysis). [0041] ❹ The prepared organic phosphating polymer is used as an active material, using polytetrafluoroethylene as a binder, acetylene black and conductive graphite as a conductive agent (in which the mass ratio of acetylene black and conductive graphite is 1:1), ethanol As a dispersant, nickel foam is used as a current collector to form an electrode, wherein various substances are organic phosphating polymers by mass ratio: binder: conductive agent: dispersant=8:10:5:5, using metal lithium as a counter electrode, A mixed solution of 1 mol/L (mol/L) of lithium hexafluorophosphate (LiPFe) in ethylene carbonate, diethyl carbonate and dimethyl carbonate is used as an electrolyte, wherein ethylene carbonate, diethyl carbonate and carbonic acid The volume ratio of methyl ester is 1: 1 : 1, and the separator is made of celgard 2400 to form a battery. 8〜2. 8 V。 The open circuit voltage of the battery is about 2. 6~2. 8 V. 098143825 Form No. A0101 Page 11 of 24 0982075059-0 201123593 [0042] The charge and discharge curves and cycle performance of the phosphatized polymer prepared from the present embodiment and the lithium metal sheet constituent half-cell are shown in FIGS. 1 and 2. Fig. 1 shows a typical charge and discharge curve of the organic phosphating polymer prepared by the present embodiment as an electrode active material for a lithium battery. The abscissa indicates the battery charge and discharge capacity (mAh/g), and the ordinate indicates the battery voltage (V). Figure 1 shows that the half-cell charge-discharge coulombic efficiency exceeds 95% during cycling. Fig. 2 is a graph showing a typical battery cycle performance curve when the organic phosphating polymer prepared in this example is used as an electrode material for a lithium battery. 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 1 200 mAh/g, and after 11 charge and discharge cycles, the capacity is still higher than 500 mAh/g. Example 2 [0044] A method for preparing an organophosphorus polymer for electrochemically reversible lithium storage, the method comprising the following steps: (1) uniformly mixing the polyethylene gas with the elemental phosphorus to obtain a The aggregated ethylene form is granules, and the mass ratio of the polyethylene gas to the red phosphorus is 0.5, and the mass ratio of the polyethylene gas to the red phosphorus is 0.5, and the mass ratio of the polyethylene gas to the red phosphorus is granules. Mw=62000, Mn=35000, and elemental phosphorus is red phosphorus, the purity is greater than industrial purity; [0046] (2) The mixture in the above step is heated and dried under a dry argon atmosphere, the drying temperature is 80 ° C, the drying time 8 hours; [0047] (3) The dried mixture is placed in a closed reaction vessel, filled with an inert gas of argon, heat treatment, heat treatment temperature of 400 ° C, heat treatment time of 8 hours, red during heat treatment Phosphorus gasification, the gasification of ethylene occurs off 098,143,825 Form No. A0101 Page 12 / Total 24 pages 0992075059-0 201123593 Hydrogen phosphating reaction, the product after heat treatment is obtained and cooled to the chamber with the reactor, Tian · / orphan, [ 0048] (4) will be hot The treated product is immersed in an aqueous ammonia solution to remove residual phosphorus; and [0049] (5) neutralizing the product of step (4) with an aqueous solution of sulfuric acid and washing the product with deionized water to neutrality after washing, and washing The latter product was dried at 80 ° C for a period of 12 hours to give an organic phosphating polymer.有机 [0050] The organic phosphating polymer is a polymer conductive polymer, the organic phosphating polymer consists of two parts: a series of conductive polymer backbone; the other part is an electrochemically active polyphosphorus group Pm side chain And functional groups R1 and R2 which affect the physical and chemical properties of the organic phosphating polymer, and the structural units of the organic phosphating polymer are i and Ψμ ❹

098143825

201123593 The phosphating polymer backbone is an electronically conductive polymer chain, which is chemically grafted on the main chain with an electrochemically active polyphosphorus group Pm and a functional group that affects the physicochemical properties of the organophosphorus polymer to form a side chain. Wherein Pm represents a polyphosphorus group, m is an integer of 12; in the polyphosphorus group Pm, P and P are covalently bonded, and the formed Pm connects two or more conductive polymer backbones. Rl, R2 represent functional groups on the side chain of the organophosphorus polymer. These functional groups affect the physicochemical properties of the organic phosphating polymer by changing the distribution of the conjugated electrons of the conductive high molecular polymer chain. In this example, both R1 and R2 As the hydrogen group, the degree of polymerization of the organophosphorus polymer is less than or equal to the degree of polymerization of the polymer precursor (polyvinyl chloride), wherein the weight percentage of phosphorus is about 75% (determined by elemental analysis). [0051] Further, the adjacent polybroken group Pm side bonds of the organically filled polymer may also be connected to each other to form 098143825

Less * species. Form No. A0101 Page 14 of 24 0982075059-0 201123593 [0055] [0055] [0057] The prepared organic phosphating polymer and conductive graphite, acetylene black, poly Vinylidene fluoride (PVDF) was mixed at a mass ratio of 8 : 5 : 5 : 1 Torr, using ethanol as a dispersant, and the mixture was adjusted into a paste, which was scraped on a copper foil to prepare an electrode, and the electrode pole piece was vacuumed. Under the condition of K12 (TC drying for 24 hours, then 'using a metal clock as the counter electrode, using a mixed solution of 1 mol/L Lip% in ethylene carbonate, diethyl carbonate and dimethyl carbonate as the electrolyte, wherein The cycle of the battery is about 2. 6~2. 8V. Cyclic performance. The open circuit voltage of the battery is about 2. 6~2. 8V. In the test, the initial discharge specific capacity exceeds 1..〇...|)〇111 at |1/8. After 1揭 charge and discharge, the capacity is still higher than 450mAh/gb. Example 3 One is used for electrification A method for preparing a reversible lithium-storing organic phosphating polymer, the method comprising the steps of: (1) combining poly-1-propylene and elemental phosphorus Evenly mixed, the method of mixing in this embodiment is to dissolve the polysilicon gas (tetra) with tetrahydroanthracene into a solution and then react with the red disc powder, wherein the mass ratio of the poly- 1 gas propylene to the red phosphorus is 1:1. The form of poly 1 gas propylene is particle ' Mw = 6 〇〇〇〇, Μ η = 32 〇〇〇, elemental phosphorus is red phosphorus, the purity is greater than industrial purity; (2) vacuum heating the mixture in the above step, the drying temperature is fine . c 'drying time is 4 hours; (= the dry mixture is placed in the reaction dad of (4), heat treated with inert gas argon, heat treatment temperature is 42 generations, heat treatment time] red phosphorus gasification during heat treatment , red dish and poly propylene 098143825 Form No. 101 0101 Page 15 / Total 24 page 0992075059-0 201123593 Dehydrogenation phosphating reaction, the heat-treated product is obtained and cooled to room temperature with the reaction dad; [0058] (4 The heat-treated product is immersed in a sodium hydroxide solution to remove residual phosphorus and oxide by-products; (5) the product of step (4) is washed with deionized water to neutrality and at a temperature of 80 ° C Drying, drying time is 12 hours, to obtain an organic phosphating polymer. [0060] The organic phosphating polymer structural unit is

An alkyl group (-ch3) having a degree of polymerization of less than or equal to the degree of polymerization of the polymer precursor (poly-1-air propylene), wherein the weight of the phosphorus is 098,143,825. Form No. A0101 Page 16 of 24 0982075059-0 201123593 The content of the fraction is 63% (determined by elemental analysis).制备 [0064] The prepared organophosphorus polymer was mixed with acetylene black and polyvinylidene fluoride (PVDF) in a mass ratio of 8:1:1, using Ν-methylpyrrolidone. The dispersing agent was adjusted into a paste, and the crucible was scraped on a copper foil to prepare an electrode. The electrode pad was dried under vacuum at 120 ° C for 24 hours, and then a lithium metal plate was used as a counter electrode, and 1 mol/L of LiPFe was used in the ethylene carbonate.

A mixed solution of D, diethyl carbonate and dinonyl carbonate is an electrolyte, wherein a volume ratio of ethylene carbonate, diethyl carbonate and dinonyl carbonate is 1:1: 1, and the separator is assembled by celgard 2400. A snap-on half battery. The battery's open circuit voltage is about 2. 6~2. 8V. The initial discharge specific capacity in the cycle performance test exceeded 1 500 mAh/g. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a charge-discharge curve of an organic phosphating polymer prepared in Example 1 and a lithium metal sheet to form a half-cell; FIG. 2 is an organic phosphating polymer prepared in Example 1 and a lithium metal sheet. Cycle performance curve of the battery at half time. [Main component symbol description] None 098143825 Form number A0101 Page 17 of 24 0982075059-0

Claims (1)

201123593 Seven patent application scope: An organic phosphating polymer for electrochemical reversible lithium storage, the organic phosphating polymer is a polymer conductive polymer, the organic phosphating polymer is composed of two parts: a part is a conductive polymer The main chain; the other part is connected to the conductive polymer main chain and has an electrochemically active polyphosphorous group Pm side chain, and functional groups R1 and R2 side chains, the organic phosphating polymer structural unit is Pb Pta ri m 098143825 201123593 c-t in Pfflc-c R2 One or more, in the polyphosphorus group, P and P are covalently bonded, in is an integer of 12; R1 and R2 are methyl, chloromethyl, dichloroindenyl, difluoroanthracene One or more of a group, a fluoroindenyl group, an ether group, a fluorine group, a gas group, a cyano group, a stupid group, an amino group, and a hydrogen group. The organic phosphating polymer for electrochemically reversible lithium storage according to claim 1, wherein the polyphosphorus group connects two or more conductive polymer backbones. The organic phosphating polymer for electrochemically reversible lithium storage according to claim 1, wherein the organic phosphating polymer has a phosphorus content of 10% to 85% by weight.有机 An organic phosphating polymer for electrochemically reversible lithium storage, the organic phosphating polymer is a polymer conductive polymer, the organic phosphating polymer consists of two parts: one part is a conductive polymer backbone; the other part a Pm side chain of a polyphosphorus group bonded to a conductive polymer backbone and having an electrochemically active polyphosphorus group, the organophosphorus polymer structural unit being In the poly-Pm Pm 11⁄2 phosphorus group, P and P are covalently bonded, and m is an integer of 12 . 098143825 Form No. A0101, page 19 of 24, pp. 09, 092, 050, 00, 00, 00, 00, 00, 00, 00, 00, 00, 00 Two or more conductive polymer backbones are connected. 6. The organic phosphating polymer for electrochemically reversible lithium storage according to claim 4, wherein the organic phosphating polymer has a phosphorus content of 56% by weight. A lithium ion battery comprising: a positive electrode, a negative electrode, and an electrolyte, wherein the active material of the negative electrode comprises the organic phosphating as described in any one of claim 1 to claim 7 polymer. The lithium ion battery according to claim 7, wherein the active material of the positive electrode is at least one of lithium cobaltate, lithium nickelate, lithium manganate, and lithium iron phosphate. 9. The lithium ion battery according to claim 7, wherein the electrolyte comprises an electrolyte salt and a solvent for dissolving the electrolyte salt, the electrolyte salt being lithium hexafluorophosphate, the solvent being methylene carbonate or ethylene carbonate. At least one of propylene carbonate, dinonyl carbonate, diethyl carbonate, dipropyl carbonate, and cesium carbonate. 10. The lithium ion battery according to claim 7, wherein the lithium ion battery has an electrochemical specific capacity of 250 mAh/g to 1 500 mAh/g. 11. A method for preparing an organophosphorus polymer for electrochemically reversible lithium storage, comprising the steps of: (1) uniformly mixing an organic polymer with elemental phosphorus to form a mixture, wherein the organic polymer in the mixture The mass ratio of the elemental phosphorus is 0.1 to 4; (2) heating the mixture under an inert atmosphere or under vacuum; (3) placing the dried mixture in a closed reaction vessel, filling with an inert gas, and performing heat treatment , the heat treatment temperature is 250 ° C ~ 600 ° C, so that the elemental phosphorus 098143825 Form No. A0101 Page 20 / 24 pages 0992075059-0 201123593 gasification, and the organic polymer dehydrogenation phosphating reaction, after heat treatment The product was cooled to room temperature with the reaction vessel; (4) the heat-treated product was immersed in an alkaline solution; and (5) the product soaked in the alkaline solution was adjusted to neutrality and dried. 12. The method for preparing an organophosphorus polymer for electrochemically reversible lithium storage according to claim 11, wherein the organic polymer is polyethylene, poly 1,2-ethylene oxide, poly One or more of vinylidene dioxide, polystyrene, polytetrafluoroethylene, polyvinylidene fluoride, polyvinylidene fluoride, polystyrene, polyethylene oxide, polyacrylonitrile and polymethyl methacrylate. The method for producing an organic phosphatized polymer for electrochemically reversible lithium storage according to claim 11, wherein the organic polymer has a form of powder, small fragments, particles or fibers. The method for producing an organic phosphatized polymer for electrochemically reversible lithium storage according to claim 11, wherein the elemental phosphorus is red phosphorus. The method for producing an organophosphorus polymer for electrochemically reversible lithium storage according to claim 11, wherein the inert gas is argon or nitrogen, and the inert atmosphere is argon or nitrogen. atmosphere. The method for producing an organophosphorus polymer for electrochemically reversible lithium storage according to claim 11, wherein the alkaline solution is aqueous ammonia, aqueous sodium hydroxide solution and aqueous solution of oxidized bell One or several of them. The method for preparing an organophosphorus polymer for electrochemically reversible lithium storage according to claim 11, wherein the step (5) comprises: neutralizing the solution after being soaked with an alkaline solution with an acidic solution; Product; and washing the product with deionized water until the washed deionized water is neutral; and drying the washed product. 18. Organic 0982075059-0 for electrochemical reversible lithium storage as described in claim 17 098143825 Form No. A0101 Page 21 of 24 201123593 A method for preparing a phosphatized polymer, wherein the drying temperature of the step (5) is from 50 ° C to 100 ° C, and the drying time is from 6 hours to 48 hours. The method for producing an organophosphorus polymer for electrochemically reversible lithium storage according to claim 17, wherein the acidic solution is one of hydrofluoric acid aqueous solution, hydrochloric acid aqueous solution, and sulfuric acid aqueous solution or Several. The method for producing an organophosphorus polymer for electrochemically reversible lithium storage according to claim 11, wherein the mixing method is grinding, ball milling or the organic polymer in a solvent After being dissolved as a solution, it is mixed with the elemental phosphor powder. The method for producing an organophosphorus polymer for electrochemically reversible lithium storage according to claim 20, wherein the solvent is acetonitrile, acetone, N,N-dimethylamine One or more of N-methyl 0-doxone, tetrahydrofuran, water and ethanol. The method for preparing an organophosphorus polymer for electrochemically reversible lithium storage according to claim 11, wherein the drying temperature of the step (2) is 50 ° C to 120 ° C, and dried. The time is 8 hours to 48 hours. ❹ 098143825 Form No. A0101 Page 22 of 24 0982075059-0