A polymer material for lithium batteries

Abstract

The application provides a polymer material for a lithium battery. The structure of the polymer material comprises at least a -[M1-M2]- polymer unit as shown in formula 1. The polymer material provided by the application contains a phosphorus group, and can be flexibly applied to a battery to improve the safety of the battery, improve the ion transmission of the battery, improve the cycle stability of the battery, and prolong the service life of the battery.

Description

Technical Field

[0001] This application relates to the field of battery technology, and in particular to a polymer material for lithium batteries. Background Technology

[0002] Lithium-ion batteries (LIBs) possess advantages such as high energy density, long cycle life, low self-discharge rate, and no memory effect, making them promising for widespread application in the field of new energy electric vehicles. With the continuous development of science and technology, the performance requirements for lithium-ion batteries are becoming increasingly stringent, and as battery energy density continues to rise, safety issues are becoming increasingly prominent. Traditional LIBs primarily use liquid electrolytes, which contain large amounts of flammable organic carbonate solvents, easily leading to safety problems such as electrolyte leakage, thermal runaway, or explosions. Polymer solid electrolytes offer advantages such as light weight, flexibility, and ease of processing, addressing the safety issues associated with liquid electrolytes. However, polymer solid electrolytes also suffer from a series of problems, including low room-temperature ionic conductivity and high interfacial impedance.

[0003] Gel polymer electrolytes (GPEs) are formed by the swelling of a polymer matrix and a plasticizer. They not only possess the high ionic conductivity of liquid electrolytes, but the polymer matrix in GPEs also forms a cross-linked structure through chemical bonds or physical forces, acting as a skeletal support. This immobilizes the fluid solvent molecules within the polymer gel skeleton, resulting in a non-flowing, semi-solid electrolyte that is easy to process and less prone to leakage, thus improving battery safety. Therefore, gel polymer electrolytes (GPEs) that can balance interfacial contact and ionic conductivity have received widespread attention and extensive research in recent years.

[0004] The plasticizers used in gel polymers are basically common liquid electrolytes or organic carbonate solvents. For example, CN108682863A discloses a lithium battery polymer gel electrolyte, which uses epoxy oleate and dimethyl carbonate as plasticizers. Although it can achieve excellent ionic conductivity, a large amount of flammable carbonate plasticizers are present in the polymer matrix, making the lithium battery constructed with it still have the potential risk of combustion and explosion. Therefore, it is difficult to completely solve the safety problem of high energy density batteries. Summary of the Invention

[0005] In view of this, embodiments of this application provide a polymer material for lithium batteries to address the technical deficiencies existing in the prior art.

[0006] This application provides a polymer material for lithium batteries, the polymer material having a structure comprising at least the [M1-M2]-polymer units as shown in Formula 1:

[0007]

[0008] M1 is selected from C, N, P, S, and Si, and M2 is selected from C, O, N, P, S, and Si.

[0009] R1-R4 are independently selected from any chain or ring that is unsubstituent, contains substituents, or has no substituents. When R1 is selected from a chain that contains substituents or has no substituents, the chain is a pure carbon chain or a carbon chain containing only one type of heteroatom. "Contains only one type of heteroatom" means that the chain may contain one or more heteroatoms, but all heteroatoms contained therein are of the same kind. For example, it may contain one or more oxygen atoms but no other heteroatoms.

[0010] R5-R6 are independently selected from any of the following: chains or rings with or without substituents, and polymeric units formed based on chains or rings; where R5 and / or R6 represent polymeric units, they include -[M1-M2]- polymeric units or other polymeric units different from -[M1-M2]-; if the polymer material structure is unfolded, the individual -[M1-M2]- polymeric units are arranged in a block manner, an alternating manner, a periodic manner, a gradient manner, or a random manner with the individual other polymeric units.

[0011] R5 and / or R6 are selected from chains or rings with or without substituents, and represent end groups of polymer materials formed based on the residues after the reaction of the raw materials or initiator.

[0012] A1 indicates that the ring structure can be substituted by a substituent at any position;

[0013] m is selected from 0.01 to 1, such as 0.02, 0.05, 0.1, 0.2, 0.3, 0.5, 0.8, and 1. It represents that there is one [M1-M2]-aggregation unit in every 1 / m [M1-M2]-aggregation units. Connected to M1 or M2. When m is 1, it can be omitted.

[0014] p is selected from integers between 10 and 10000, such as 10, 20, 50, 80, 100, 500, 1000, 2000, 3000, 5000, 6000, 8000, and 10000. The structure of its representation 1 contains p -[M1-M2]-aggregate units.

[0015] This application innovatively incorporates [a specific ingredient] into polymer materials. The polymeric structure can improve battery safety, enhance ion transport, increase cycle stability, and extend battery life.

[0016] Specifically, if R1-R6 are independently selected from chains, the chains are chains of 1 to 15 atoms, preferably chains of 1 to 10 atoms, more preferably chains of 2 to 6 atoms, including saturated carbon chains, unsaturated carbon chains, saturated heterochains, and unsaturated heterochains; the atoms on the chains are selected from C, S, N, O, P, B, or Si.

[0017] If R1-R6 independently contain rings, the rings are three to eighteen-membered rings, preferably four to ten-membered rings, and more preferably five to eight-membered rings, such as five-membered rings, six-membered rings, etc. The rings include monocyclic rings, fused rings, bridging rings, or spirocyclic rings, and the atoms on the rings are selected from C, P, S, Si, N, or O. The monocyclic rings include saturated carbon rings, unsaturated carbon rings, saturated heterocyclic rings, unsaturated heterocyclic rings (-C=O), aromatic carbon rings, and aromatic heterocyclic rings.

[0018] The substituents include: H, halogen atoms, =O, =S, alkyl, heteroalkyl, alkenyl, heteroalkenyl, alkynyl, heteroalkynyl, hydroxyl, carbonyl, aldehyde, carbonate, haloformyl, carboxyl, ester, peroxy, amine (primary amine, secondary amine, tertiary amine, quaternary ammonium salt), imino (C=N), imide (C(=O)NC(=O)), azo, nitrate ester (RONO2), phosphate ester, thioether, disulfide, cyano, sulfonic acid, sulfonyl, amide, nitro, pyridyl, acyloxy, phenyl, benzyl, benzyloxy, phenoxy, acetyl, benzoyl, benzyloxycarbonyl, and chains or rings containing the above groups. Any H in the above substituents may be substituted with a halogen, preferably with F.

[0019] Optionally, R3-R4 are independently selected from any one of the following: none, saturated carbon chains consisting of 1 to 10 carbon atoms, or unsaturated carbon chains.

[0020] In this case, at least one P atom is connected to a C atom in the chain. Compared to all P atoms having all their bonds connected to heteroatoms or directly to rings, this arrangement is more conducive to the function of the phosphorus group and helps to improve the safety of polymer materials.

[0021] Optionally, R1 contains at least one unsaturated bond and / or at least one heteroatom, wherein the unsaturated bond includes a double bond or a triple bond, and the heteroatom includes N, O, P, S, Si, or F;

[0022] Preferably, the unsaturated bond is =O;

[0023] More preferably, R1 contains at least one R1 can also contain multiple

[0024] In this context, -O is directly connected to P or M1 or indirectly connected through a chain and / or a ring, and -C=O is directly connected to P or M1 or indirectly connected through a chain and / or a ring. The limitations regarding chains and rings here are detailed above and will not be repeated here.

[0025] The presence of ester groups between P and the double bond can effectively improve the battery's electrochemical performance, such as initial efficiency and capacity retention, as well as enhance battery safety and extend battery life.

[0026] Optionally, R1 is selected from -O or -C=O is directly connected to P;

[0027] Preferably, -C=O and M1 are indirectly connected through a chain consisting of 1-10 atoms;

[0028] More preferably, -C=O and M1 are indirectly linked through a chain of 2-8 atoms. This arrangement helps to improve the mechanical properties of the material itself.

[0029] The polymer material as claimed in claim 1, wherein R3 is selected from... OR, where R is selected from any one of H, Li, halogen atoms, chains or rings with or without substituents;

[0030] Preferably, the OR is OLi;

[0031] Preferably, the chain or ring containing or without substituents is a chain or ring composed of 1-8 atoms;

[0032] Optionally, R3 is selected from OR, where R is selected from any one of H, Li, halogen atoms, chains or rings with or without substituents;

[0033] Preferably, the OR is OLi;

[0034] Preferably, the chain or ring containing or without substituents is a chain or ring composed of 1-8 atoms;

[0035] R3 is preferred The ring structure in the substituents directly bonded to the P atom can improve the ability to suppress battery temperature rise, thereby making the battery safer.

[0036] Preferably, the substituent represented by A1 is replaced by one or more halogen atoms, preferably by F.

[0037] Preferably, the halogen atom is F, and the chain contains at least one heteroatom.

[0038] Optionally, the The ring structure represented is selected from single rings or multiple rings. The single ring is selected from 3-12 saturated carbon rings, saturated heterocycles, unsaturated carbon rings or unsaturated heterocycles. The multiple rings are selected from fused rings, bridged rings, spiral rings or linked rings formed by combining any two of the single rings based on the single ring.

[0039] Preferably, the monocyclic ring is selected from five- or six-membered unsaturated carbon rings or unsaturated heterocyclic rings;

[0040] More preferably, the monocyclic ring is selected from five- or six-membered unsaturated heterocyclic rings.

[0041] Optionally, R5 or R6 is selected from the -[M3-M4]-polymer unit, the structure of which is shown in Equation 2:

[0042]

[0043] The structure of the polymer material is selected from:

[0044] Among them, M3 is selected from C, N, P, S, and Si, and M4 is selected from C, O, N, P, S, and Si;

[0045] R 10 -R 14 Independently selected from any one of chains or rings that are unsubstituted, contain substituents, or do not contain substituents;

[0046] n is selected from an integer between 5 and 1000, such as 10, 20, 30, 50, 80, 100, 150, 200, 250, 300, 350, 400, 450, 500, 600, 800, 900, 1000, etc., preferably 10-800, indicating that there are n -[M3-M4]-aggregate units in the structure.

[0047] When the polymer material structure is unfolded, individual -[M1-M2]-polymer units and individual -[M3-M4]-polymer units are arranged in a block manner, an alternating manner, a periodic manner, a gradient manner, or a random manner.

[0048] Alternatively, H1 can be used to represent a monomer unit constituting the -[M1-M2]-polymer unit. Let H2 represent a monomer unit that constitutes the -[M3-M4]-polymer unit. The "—" drawn to the left of M1 and M3 and to the right of M2 and M4 in the H1 and H2 monomer units indicates that they are connected to other H1 or H2 monomer units through this bond, and is not an abbreviation of -CH3.

[0049] In polymer materials, the arrangement of H1 and H2 includes:

[0050] Arranged in a segmented manner: In this case, the first H1 represents one or more repeating permutations, the second one. H2 represents one or more repeating permutations;

[0051] Arranged in an alternating manner: one or more H1s are alternated with one or more H2s in sequence, for example... (Alternating between H1 and H2), (Two H1s and one H2 are arranged alternately), (Alternating arrangements of three H1s and one H2) are all acceptable, and will not be elaborated further here. In this case, "Indicates one or more repetitions" indicates one or more.

[0052] Arranged in a periodic manner: multiple periods are formed by one or more H1 and one or more H2, and the multiple periods are arranged sequentially; for example... Equals are acceptable; one set of parentheses represents one cycle. It indicates one or more repeating periods.

[0053] Arranged in a gradient manner: the composition of H1 and H2 gradually changes along the chain; for example... H1 and H2 represent H1 and H2 as the chain gradient increases.

[0054] Irregular arrangement: One or more H1s and one or more H2s are arranged in any alternating pattern. For example... All of the above are acceptable, and will not be elaborated further here. In this case, This indicates an irregular repetition of H1 and H2.

[0055] Optionally, R 14 Selected from a ring or chain containing at least one heteroatom, wherein any position of the ring or chain can be substituted by a substituent;

[0056] Preferably, R 14 Selected from a ring or chain containing at least two heteroatoms, wherein the ring or chain contains at least one =O;

[0057] More preferably, R 14 Selected from:

[0058] In this context, A1 and A2 indicate that atoms on the ring / chain can be substituted by substituents.

[0059] It should be noted that, in the technical solutions provided in this application, regardless of the synthesis method or process used, polymer materials as shown in Formula 1 can be formed through the reaction of raw material A itself or the reaction between raw material A and raw material B. If, under certain special circumstances, raw material A itself or the reaction between raw material A and raw material B yields other products, these products are also within the scope of protection of this application.

[0060] Optionally, in the structure of the polymer material, m is selected from 0.1-1, p is selected from an integer between 30 and 8000, n is selected from an integer between 10 and 800, and p > n.

[0061] Optionally, the polymer material is prepared at least based on the reaction of raw material A, or at least based on the reaction of raw material A and raw material B;

[0062] The structure of raw material A is as follows: The structure of raw material B is as follows:

[0063] This application also provides an electrolyte comprising the polymer material as described above, or comprising the raw materials for preparing the polymer material as described above.

[0064] This application also provides a battery comprising any one or more of the following: the polymer material as described above, the raw material for preparing the polymer material as described above, and the electrolyte as described above.

[0065] Optionally, the battery can be a liquid battery, a hybrid solid-liquid battery, or an all-solid-state battery, wherein hybrid solid-liquid batteries and all-solid-state batteries are collectively referred to as solid-state batteries.

[0066] This application also provides an application of the polymer material as described above in a battery, wherein the polymer material is placed in the battery assembly or cell of the battery, and the battery is prepared by a non-in-situ curing process;

[0067] Alternatively, the raw materials used to prepare the polymer material may be placed in the battery assembly or cell of the battery, and the battery may be prepared by in-situ curing process;

[0068] The battery assembly includes electrodes, a separator, and an electrolyte membrane.

[0069] Optionally, placing the polymer material in the battery via a non-in-situ curing method includes:

[0070] (1) Placing the polymer material in the cell of the battery, comprising:

[0071] The polymer material is first dissolved in the electrolyte and then injected into the prepared battery cell;

[0072] (2) Placing the polymer material in the battery assembly of the battery, comprising:

[0073] The polymer material is dissolved in a solvent and then coated onto an electrode sheet, separator, or formed into a film separately to form an electrode sheet, separator, or electrolyte membrane with a polymer material coating; or the polymer material is mixed into positive and negative electrode slurries to form an electrode sheet containing polymer material.

[0074] Optionally, the solvent includes one or more of the following: ethylene carbonate, fluoroethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, butenyl carbonate, methyl propyl carbonate, methyl formate, ethyl formate, propyl formate, butyl formate, ethyl acetate, propyl acetate, butyl acetate, methyl propionate, ethyl propionate, butyl propionate, methyl butyrate, ethyl butyrate, propyl butyrate, 8-valerolactone, tetrahydrofuran, 2-methyltetrahydrofuran, 4-methyl-1,3-dioxolane, 2-methyl-1,3-dioxolane, ethylene glycol dimethyl ether, and 1,3-dioxolane, sulfolane, and dimethyl sulfoxide.

[0075] In the process of dissolving the polymer material in a solvent, an auxiliary agent is also added, which includes any one or more of the following: lithium salt, inorganic oxide particles, and fast ion conductor.

[0076] The lithium salt is selected from one or more of lithium trifluoromethanesulfonate (LiCF3SO2), lithium bis(trifluoromethanesulfonate)imide (LiN(CF3SO2)2), lithium hexafluorophosphate (LiPF6), lithium tetrafluoroborate (LiBF4), lithium perchlorate (LiClO4), lithium dioxaborate (LiBOB), lithium difluorooxaborate (LiDFOB), lithium chloride (LiCl), lithium iodide (LiI), lithium bis(fluorosulfonylimide) (LiFSI), and lithium hexafluoroarsenate (LiAsF6).

[0077] The inert inorganic particles are selected from SiO2, ZrO2, Al2O3, TiO2, BaTiO3, CeO2, CuO, ZnO, MnO, MnO2, silicates, aluminosilicates, borosilicates, and formula A. x B y O z The oxoacid salt consists of at least one inorganic particle from the group consisting of oxoacid salts, or any of the above-mentioned functionalized inorganic particles, wherein A is an alkali metal or alkaline earth metal, B is selected from the group consisting of Al, Mn, Si, Ti, Zn, Zr, Fe and Cu, and x, y, z are the corresponding numbers of atoms such that the total charge of the oxoacid salt is 0.

[0078] The active fast ion conductor is an oxide solid electrolyte, and the oxide solid electrolyte particles include any one or a combination of at least two of the following compounds: Li1+x1Alx1Ge2-x1(PO4)3 with NASICON structure or its isomorphous heteroatom-doped compound, Li1+x2Alx2Ti2-x2(PO4)3 or its isomorphous heteroatom-doped compound, Li3x3La 2 / 3 -x3TiO3 or its isomorphous heteroatom-doped compound, Li 3 / 8 Sr 7 / 16 Ta 3 / 4 Hf 1 / 4 O3 or its isomorphous heteroatom-doped compound, Li2x4-y1Sr1-x4Tay1Zr1-y1O3 or its isomorphous heteroatom-doped compound, Li with inverse perovskite structure 3-2 x5Mx5Ha l O, Li3OCl or its isomorphous heteroatom-doped compound, 2Li4-x6Si1-x6Px6O4 with LISICON structure or its isomorphous heteroatom-doped compound, Li 14 ZnGe4O 16 or its isomorphous heteroatom-doped compound, Li7-x7La3Zr2-x7O with garnet structure 12 or its isomorphous heteroatom-doped compound, where 0 < x1 ≤ < x crystal form, 0 < x2 ≤ < x crystal, 0.06 type different 3 ≤.06 type, 0.25 type different 1 ≤., x4 = 0.75y1, 00.5 ≤ 0.75, 0.5756 ≤.57; 0.57 < 1; where M includes Mg 2+ 、Ca 2+ 、Sr 2+ 或Ba 2+ 中的任意一种或至少两种的组合,Hal为元素Cl或I。

[0079] Optionally, the in-situ curing method of placing the raw materials in the battery includes:

[0080] (1) Placing the raw materials in the battery cell, which includes:

[0081] Adding the raw materials and the initiator to the electrolyte, and forming an integrated solid-state battery of the cell by in-situ curing; or pre-setting at least one of the raw materials in the battery component, adding the initiator and the remaining raw materials to the electrolyte, and then injecting them into the prepared cell to form an integrated solid-state battery of the cell by in-situ curing;

[0082] (2) Placing the raw materials in the battery component, which includes:

[0083] The raw materials are prepared into a precursor solution and coated onto an electrode sheet, diaphragm, or formed into a film on its own, and then cured in situ to form an electrode sheet, diaphragm, or electrolyte membrane with a polymer material coating.

[0084] Optionally, when the raw materials include raw material A and raw material B, the molar ratio of raw material B to raw material A is 0 to 1, such as 0, 0.1, 0.2, 0.5, 0.8, 0.9, 1, etc., and the total mass of raw material A and raw material B accounts for 1% to 50% of the total mass of the precursor solution. Preferably, it is 1% to 10%, more preferably 1% to 5%, such as 1%, 2%, 3%, 4%, 5%, etc. The precursor solution can be obtained by uniformly mixing lithium salt, additives, organic solvent, raw material A, raw material B, and initiator at a dew point below -45°C.

[0085] The mass fraction of lithium salt in the precursor solution is 5% to 30%, preferably 10% to 25%, and more preferably 15% to 20%.

[0086] The organic solvent is one or more combinations of ethylene carbonate, fluoroethylene carbonate, vinylene carbonate, ethylene ethylene carbonate, propylene carbonate, butene carbonate, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, methyl propyl carbonate, methyl formate, ethyl formate, propyl formate, butyl formate, ethyl acetate, propyl acetate, butyl acetate, methyl propionate, ethyl propionate, butyl propionate, methyl butyrate, ethyl butyrate, propyl butyrate, δ-valerolactone, tetrahydrofuran, 2-methyltetrahydrofuran, 1,3-dioxolane, 4-methyl-1,3-dioxolane, 2-methyl-1,3-dioxolane, ethylene glycol dimethyl ether, polyethylene glycol, sulfolane, triethylene glycol dimethyl ether, fluorinated 1,4-dimethoxybutane, bis(2,2,2-trifluoroethyl) ether, tetramethylsilane, and tetraethylene glycol dimethyl ether.

[0087] The organic solvent has a mass fraction of 1% to 90% in the precursor solution, preferably 10% to 80%, more preferably 20% to 60%, such as 30%, 40%, 50%, etc.

[0088] The initiator is one or more of the following: azobisisobutyronitrile (AIBN), azobisisoheptanenitrile (ABVN), dimethyl azobisisobutyrate (AIBME), benzoyl peroxide (BPO), tert-butyl peroxide (BPB), methyl ethyl ketone peroxide, or a composite initiator system (such as AIBN-ABVN or BPO-BPB).

[0089] The initiator has a mass fraction of 0.001% to 0.5% in the precursor solution, preferably 0.005% to 0.3%, more preferably 0.01% to 0.2%, such as 0.015%, 0.05%, 0.1%, 0.15%, etc.

[0090] The additives include one or more combinations of fluoroethylene carbonate, vinylene carbonate, trimethyl phosphate, triethyl phosphate, succinic anhydride, 18-crown ether-6, triphenyl phosphite, ethylene ethylene carbonate, trimethyl borate, lithium difluorobis(oxalato) phosphate, lithium tetrafluoro(oxalato) phosphate, tributyl phosphate, biphenyl, vinyl sulfite, difluorodiphenylsilane, lithium difluorosulfonylimide, tributyl borate, ethoxypentafluorocyclotriphosphazene, vinyl sulfate, lithium nitrate, 1,3-propanesulfonyl lactone, lithium difluorophosphate, diethyl sulfite, and succinic anhydride.

[0091] The battery cell includes a positive electrode, a negative electrode, and a separator disposed between the positive electrode and the negative electrode.

[0092] Optionally, the positive electrode active material may include one or more of lithium iron phosphate, lithium iron manganese phosphate, lithium cobalt oxide, lithium manganese oxide, lithium nickel manganese oxide, lithium nickel cobalt manganese oxide, lithium nickel cobalt aluminum oxide, and lithium-rich manganese; the negative electrode active material may include one or more of graphite, silicon, soft carbon, hard carbon, silicon-carbon composite material, silicon-oxygen-carbon, lithium titanate, mesophase carbon microspheres, molybdenum disulfide, silicon suboxide, silicon, lithium metal, or lithium metal alloy; the separator may be one of polyolefin separator, cellulose separator, polyimide separator, polyamide separator, aramid separator, PET nonwoven separator, ceramic coated separator, solid electrolyte coated separator, and PVDF coated separator.

[0093] In practical applications, the electrolyte can be a commercially available electrolyte for lithium secondary batteries, or it can be formulated independently. The present invention does not have any particular limitations on its composition and ratio.

[0094] Technical effects:

[0095] This application innovatively provides a polymer material containing phosphorus groups, which can be flexibly applied in batteries to improve battery safety, enhance battery ion transport, improve battery cycle stability, and extend battery life.

[0096] The polymer material provided in this application contains a special structure as shown in Formula 1. Solid-state batteries prepared by non-in-situ curing or in-situ curing methods greatly improve the safety and cycle stability of the battery.

[0097] Furthermore, the in-situ solidification method can significantly improve the interfacial contact between battery materials (such as electrolytes) and electrodes, reducing polarization and interfacial impedance. This, in turn, enhances the battery's energy density, cycle life, and other electrical properties, greatly improving its electrochemical performance and extending its lifespan. The in-situ solidification process is simple, safe, and environmentally friendly, significantly reducing the use and emissions of organic solvents. It is compatible with existing liquid battery processes, facilitating rapid industrialization. Compared to non-in-situ solidification processes, in-situ solidification can better improve battery safety and electrochemical performance. Attached Figure Description

[0098] Figure 1 This is a comparison graph of the battery cycle curves of Test Example 1 in this application;

[0099] Figure 2 This is a comparison chart of the battery nail penetration test results for Test Example 2 of this application. Detailed Implementation

[0100] The specific embodiments of this application are described below with reference to the accompanying drawings.

[0101] In this invention, unless otherwise stated, scientific and technical terms used herein have the meanings commonly understood by those skilled in the art. Furthermore, the reagents, materials, and procedures used herein are all widely used in the relevant fields. To better understand this invention, definitions and explanations of related terms are provided below.

[0102] In the embodiments of this application, the degree of polymerization p and n of the polymeric unit in the polymer material structure can be calculated using the number-average molecular weight method.

[0103] Number-average molecular weight (Mn) is the most commonly used method for calculating the degree of polymerization. Polymer materials are composed of polymeric units with the same chemical composition but different degrees of polymerization. The number-average molecular weight (Mn) is obtained by statistically averaging the number of molecules. Number-average molecular weight = (Molecular weight of each component * Number of moles of each component) / Total number of moles. The formula for calculating number-average molecular weight is existing technology and will not be elaborated further here.

[0104] The 1H NMR spectrum in this embodiment 1 In 1H NMR, s represents a singlet, d represents a doublet, t represents a triplet, q represents a quartet, m represents a multiplet (multiplets greater than four, such as quintets, sextets, etc.), dd represents a doublet, and dt represents a doublet. The number before the parentheses indicates the chemical shift, and the number before the H in the parentheses indicates the number of H atoms. For example, 2.22(s, 2H) means that there are two H atoms with a chemical shift of 2.22, and the peak appears as a singlet. Other cases can be deduced similarly and will not be elaborated further.

[0105] In this embodiment, MS(ESI)m / z example (MH) + This indicates mass spectrometry.

[0106] In the embodiments of this application, the corresponding substances for the English abbreviations are as follows: ethyl methyl carbonate (EMC), diethyl carbonate (DEC), ethylene carbonate (EC); lithium nitrate (LiNO3), fluoroethylene carbonate (FEC), ethylene sulfate (DTD), lithium tetrafluorooxalate phosphate (LiPC2O2F4), 1,3-propane sulpholol (1,3-PS), lithium difluorophosphate (LiPO2F2), vinylene carbonate (VC); lithium difluorooxalate borate (LiODFB), lithium hexafluorophosphate (LiPF6), lithium difluoromethanesulfonyl imide (LiFSI); azobisisobutyronitrile (AIBN), benzoyl peroxide (BPO).

[0107] In the embodiments of this application, 0.5C / 0.5C means charging at a rate of 0.5C and discharging at a rate of 0.5C.

[0108] In this application, polymer materials can be placed in the battery assembly or cell of the battery, and the battery can be prepared by a non-in-situ curing process;

[0109] Alternatively, the raw materials used to prepare the polymer material may be placed in the battery assembly or cell of the battery, and the battery may be prepared by an in-situ curing process. The battery assembly includes electrodes, a separator, and an electrolyte membrane.

[0110] The non-in-situ curing method of placing the polymer material in the battery includes:

[0111] (1) Placing the polymer material in the battery cell; specifically including: dissolving the polymer material in the electrolyte first, and then injecting it into the prepared battery cell;

[0112] (2) Placing the polymer material in the battery assembly of the battery; specifically including:

[0113] The polymer material is dissolved in a solvent and then coated onto an electrode sheet, separator, or formed into a separate film to form an electrode sheet, separator, or electrolyte membrane with a polymer material coating; or the polymer material is mixed into positive and negative electrode slurries to form an electrode sheet containing polymer material.

[0114] The method of placing the raw material in the battery for in-situ curing includes:

[0115] (1) The raw materials are placed in the cell of the battery; specifically, the raw materials and initiator are added to the electrolyte and solidified in situ to form a solid-state battery with integrated cell; or at least one of the raw materials is pre-placed in the battery assembly, the initiator and the remaining raw materials are added to the electrolyte and then injected into the prepared cell, and solidified in situ to form a solid-state battery with integrated cell.

[0116] (2) Placing the raw material in the battery assembly of the battery; specifically including:

[0117] The raw materials are prepared into a precursor solution and coated onto an electrode sheet, diaphragm, or formed into a film on its own, and then cured in situ to form an electrode sheet, diaphragm, or electrolyte membrane with a polymer material coating.

[0118] It should be noted that the application methods shown in the following embodiments are only preferred application methods for this raw material / battery material, and other in-situ curing or non-in-situ curing application methods are also applicable.

[0119] Example 1

[0120] Raw material A1: Raw material B1:

[0121] Preparation method: Raw material A1: through (CAS:79-41-4) and (CAS:1707-03-5) Under acid catalysis, esterification reaction was carried out to obtain raw material A1.

[0122] Raw material B1: Under nitrogen protection, add 0.2 mmol to a 25 mL Schlenk tube. 2 mL of dry dichloromethane was cooled to 0°C, and 0.2 mmol of acryloyl chloride was added dropwise. After the addition was complete, the mixture was stirred for 1 h, and then allowed to react at room temperature for 1 h. 5 mL of water was added, and the mixture was extracted with dichloromethane at room temperature. The organic phases were combined, washed with saturated NaCl, dried over anhydrous sodium sulfate, filtered, distilled under reduced pressure, and column chromatography was performed to obtain the final product. Under nitrogen protection, add 0.2 mmol of [agent] to a 25 mL Schlenk tube. 2 mL of dry tetrahydrofuran was cooled to -78°C, and n-butyllithium hexane solution was added dropwise. After the addition was complete, the mixture was stirred for 30 min, then cooled to room temperature and stirred for 1 h. The mixture was then distilled under reduced pressure to obtain raw material B1.

[0123] 1H NMR spectrum of raw material A1 1 H NMR (300MHz, DMSO, δδSOM): 7.72 (s, 4H), 7.46 (s, 4H), 2.01 (s, 3H), 6.43 (s, 1H), 6.18 (s, 1H).

[0124] 1H NMR spectrum of raw material B1 1 H NMR (300MHz, DMSO, δδSOM): 4.31 (q, 2H), 4.47 (t, 2H), 2.01 (s, 3H), 6.48 (s, 1H), 6.40 (s, 1H).

[0125] Application method: Add raw materials A1, B1 and initiator to the electrolyte to prepare a precursor solution, and then inject the precursor solution into the battery cell for in-situ curing.

[0126] After copolymerization of raw material A1 and raw material B1, a mixture of 200 H atoms is formed. A1 Aggregation unit and 80 H B1 Polymer materials composed of polymer units, the structure of which is mainly based on five H... A1 A polymer unit H B1 The aggregation units are arranged in an alternating manner.

[0127] Where H A1 The structure of the polymer unit is -Q1 is -CH3, -Q2 is m is 1, p is 200.

[0128] H B1 The structure of the polymer unit is -Q3 means none, -Q4 means none. n is 80.

[0129] Example 2

[0130] Raw material A2: Raw material B2:

[0131] Preparation method: Raw material A2 is an existing substance with CAS number 60421-10-5;

[0132] The preparation method of raw material B2 is the same as that of raw material A1 in Example 1. (CAS: 79-10-7) and (CAS: 1433993-67-9) The reaction yields raw material B2;

[0133] Raw material A2 MS (ESI) m / z 593.15 (MH) + Raw material B2 MS(ESI) m / z 208.00 (MH) + .

[0134] Application method: Add raw materials A2, B2 and initiator to the electrolyte to prepare a precursor solution, and then inject the precursor solution into the battery cell for in-situ curing.

[0135] After copolymerization of raw material A2 and raw material B2, a mixture of 10,000 H atoms is formed. A2 Aggregation unit and 1000 H B2 A polymer material composed of polymeric units, the structure of which is mainly arranged in a block-like manner.

[0136] Where H A2The structure of the polymer unit is -Q1 is -CH3, -Q2 is m is 1, p is 10000.

[0137] H B2 The structure of the polymer unit is -Q3 is -CH3, -Q4 is n is 1000.

[0138] Example 3

[0139] Raw material A3: Raw material B3:

[0140] Preparation method: Raw material A3 is an existing substance, Reaxys ID: 32890736, MS (ESI) m / z 540.15 (MH). + .

[0141] Raw material B3: 0.2 mmol of sulfonate substrate 1 and 2 mL of dry dichloromethane were added to a 25 mL Schlenk tube. The tube was frozen with liquid nitrogen, purged with nitrogen under vacuum, and brought to room temperature. 0.2 mmol of NBS was added under nitrogen protection. After addition, the temperature was raised to 40°C and the reaction was stirred for 8 h. The reaction was terminated, and the mixture was distilled under reduced pressure. Column chromatography yielded the intermediate with α-terminal bromine substitution of the sulfonate substrate olefin double bond. The bromine-substituted intermediate from the previous step was added to 2 mL of dichloromethane, along with benzyltriethylammonium chloride (TEBAC) and 0.2 mmol of NaF. The mixture was stirred at 40°C for 8 h. After cooling to room temperature, 5 mL of water was added, and the mixture was extracted with dichloromethane at room temperature. The organic phases were combined, washed with saturated NaCl, dried over anhydrous sodium sulfate, filtered, and distilled under reduced pressure. Column chromatography yielded the fluorinated sulfonate intermediate.

[0142] Under nitrogen protection, 0.2 mmol of intermediate 2 was added to a 25 mL Schlenk tube, followed by dropwise addition of 200 mmol of sodium dry borohydride tetrahydrofuran complex. The mixture was stirred at room temperature for 30 min. Sodium hydroxide (70 wt) was added sequentially, followed by hydrogen peroxide (30 wt). The mixture was stirred for 30 min, then 5 mL of dichloromethane and 5 mL of water were added. Extraction was performed using 3,L-alkane and dichloromethane. The organic phases were combined, washed with saturated NaCl, dried over anhydrous sodium sulfate, filtered, distilled under reduced pressure, and column chromatography was used to obtain the intermediate.

[0143] Under nitrogen protection, 0.2 mmol of the intermediate was added to a 25 mL Schlenk tube. 2 mL of dry dichloromethane was added dropwise with 0.2 mmol of acryloyl chloride. The mixture was stirred at room temperature for 30 min to terminate the reaction. 5 mL of water was added, and the mixture was extracted with dichloromethane. The organic phases were combined, washed with saturated NaCl, dried over anhydrous sodium sulfate, filtered, distilled under reduced pressure, and column chromatography was performed to obtain starting material B3. MS (ESI) m / z 224.02 (MH) + .

[0144] Application method: Add raw materials A3, B3 and initiator to the electrolyte to prepare a precursor solution, and then inject the precursor solution into the battery cell for in-situ curing.

[0145] After copolymerization of raw material A3 and raw material B3, a mixture of 250 H atoms is formed. A3 Aggregation unit and 5 H B3 A polymer material composed of polymeric units, the structure of which is mainly randomly arranged.

[0146] Where H A3 The structure of the polymer unit is -Q1 is -CH3, -Q2 is m is 1, p is 250.

[0147] H B3 The structure of the polymer unit is -Q3 is -CH3, -Q4 is n is 5.

[0148] Example 4

[0149] Raw material A4: Raw material B4:

[0150] Preparation method:

[0151] Raw material A4: Under nitrogen protection, add 0.2 mmol to a 25 mL Schlenk tube. 2 mL of dry tetrahydrofuran was cooled to -78°C, and 0.2 mmol of n-butyllithium n-hexane solution was added dropwise. After the addition was complete, the mixture was stirred for half an hour, then returned to room temperature and distilled under reduced pressure to obtain raw material A4.

[0152] Raw material B4: Under nitrogen protection, add 0.2 mmol of substrate to a 25 mL Schlenk tube. 2 mL of 1,4-dioxane was added dropwise with 0.2 mmol of liquid bromine and 3.6 μL of water. After the addition was complete, the mixture was heated to 90 °C and reacted for 6 h. 5 mL of water was added, and the mixture was extracted with 3 × 5 mL of dichloromethane. The organic phases were combined, washed with saturated NaCl, dried over anhydrous sodium sulfate, filtered, distilled under reduced pressure, and column chromatography was performed to obtain the intermediate.

[0153] Under nitrogen protection, 0.2 mmol of intermediate 4 and 2 mL of dry dichloromethane were added to a 25 mL Schlenk tube. The mixture was cooled to 0 °C, and 0.2 mmol of DAST reagent (diethylaminotrifluoride) was added. After the addition was complete, the reaction was carried out for 1 h. The mixture was then distilled under reduced pressure, and the intermediate was obtained by column chromatography. Will NaOH was added to an acetonitrile solvent containing 20% ​​water, and the mixture was heated at 80°C for 8 hours to obtain an intermediate.

[0154] Under nitrogen protection, 0.2 mmol of the intermediate was added to a 25 mL Schlenk tube. Add 1 mL of dry dichloromethane, cool to 0 °C, add freshly prepared butenoyl chloride-dichloromethane mixture dropwise, react for 1 h after addition, then return to room temperature and react for another 1 h, add 5 mL of water, extract with 3 × 5 mL of dichloromethane, combine the organic phases, wash with saturated NaCl, dry with anhydrous sodium sulfate, filter, distill under reduced pressure, and column chromatography to obtain raw material B4.

[0155] 1H NMR spectrum of raw material A4 1 H NMR (300MHz, DMSO, δδSOM): 7.24 (d, 2H), 7.31 (d, 2H), 7.26 (d, H), 2.95 (m, 2H), 4 .38(dd, 2H), 4.31(dd, 2H), 2.79(t, 2H), 2.01(s, 3H), 6.48(s, 1H), 6.40(s, 1H).

[0156] 1H NMR spectrum of raw material B4 1 H NMR (300MHz, DMSO, δδppm): 6.62 (dd, 1H), 8.07 (dd, 1H), 2.92 (d, 2H), 6.07 (m, 1H), 5.25 (s, 1H), 5.32 (t, 1H).

[0157] Application method: Add raw materials A4, B4 and initiator to the electrolyte to prepare a precursor solution, and then inject the precursor solution into the battery cell for in-situ curing.

[0158] After copolymerization, raw material A4 and raw material B4 form a group consisting of 40 H atoms. A4 Aggregation unit and 10 H B4 Polymer materials composed of polymer units, wherein the H in the structure of the polymer material A4 H B4 Mainly arranged according to cycles, 10 H A4 and 1 H B4 For one period (H) A4 -H A4 -H A4 -H A4-H A4 -H A4 -H A4 -H A4 -H A4 -H A4 -H B4 ).

[0159] Where H A4 The structure of the polymer unit is -Q1 is -CH3, -Q2 is m is 1, p is 40.

[0160] H B4 The structure of the polymer unit is -Q3 means none, -Q4 means none. n is 10.

[0161] Example 5

[0162] Raw material A5: Raw material B5:

[0163] Raw material A5 is an existing substance, CAS: 869483-26-1, MS (ESI) m / z 284.10 (MH). + .

[0164] Raw material B5 is an existing substance, CAS: 18133-42-1, MS (ESI) m / z 111.99 (MH). + .

[0165] Application method: Place raw material A5 in the positive electrode, add the initiator and raw material B5 into the electrolyte, and then inject them into the prepared battery cell for in-situ curing.

[0166] After copolymerization, raw material A5 and raw material B5 form a group consisting of 30 H atoms. A5 Aggregation unit and 30 H B5 Polymer materials composed of polymer units, wherein the H in the structure of the polymer material A5 H B5 It is mainly arranged randomly.

[0167] Where H A5 The structure of the polymer unit is -Q1 means none, -Q2 means none. m is 1, p is 30.

[0168] H B5 The structure of the polymer unit is -Q3 means none, -Q4 means none. n is 30.

[0169] Example 6

[0170] Raw material A6: Raw material B6:

[0171] Preparation method: Raw material A6 is an existing substance with CAS number 191105-63-2 and MS (ESI) m / z 368.14 (MH). + .

[0172] Raw material B6: through The intermediate was obtained through fluorination. Under nitrogen protection, 0.2 mmol of the intermediate was added to a 25 mL Schlenk tube. 2 mL of dry dichloromethane and 0.2 mmol of NBS were added, and the mixture was heated to 40 °C and stirred for 8 h to terminate the reaction. The mixture was then distilled under reduced pressure and column chromatography was used to obtain the intermediate.

[0173] Add 0.2 mmol of the intermediate to a 25 mL reaction tube. 100 μL (3M) NaOH was added, and the mixture was stirred at room temperature for 8 h to terminate the reaction. 5 mL of dichloromethane and 5 mL of water were added, and the mixture was extracted with 3 × 5 mL of dichloromethane. The organic phases were combined, washed with saturated NaCl, dried over anhydrous sodium sulfate, filtered, distilled under reduced pressure, and column chromatography was performed to obtain the intermediate.

[0174] Under nitrogen protection, 0.2 mmol of the intermediate was added to a 25 mL Schlenk tube. 2 mL of dichloromethane was cooled to 0 °C, and 0.2 mmol of acryloyl chloride was added dropwise. After the addition was complete, the reaction was allowed to proceed for 1 h, and then the mixture was allowed to return to room temperature for another 1 h. 5 mL of water was added, and the mixture was extracted with 3 × 5 mL of dichloromethane. The organic phases were combined, washed with saturated NaCl, dried over anhydrous sodium sulfate, filtered, distilled under reduced pressure, and column chromatography was performed to obtain the intermediate.

[0175] Under nitrogen protection, 0.2 mmol of intermediate 5 and 2 mL of dry tetrahydrofuran were added to a 25 mL Schlenk tube. The mixture was cooled to -78 °C, and 0.2 mmol of n-butyllithium (in n-hexane solution) was added dropwise. After the addition was complete, the reaction was allowed to proceed for 30 min, then brought to room temperature and distilled under reduced pressure to obtain starting material B6. MS (ESI) m / z 188.02 (MH) + .

[0176] Application method: Place raw material A6 in the diaphragm, add the initiator and raw material B5 to the electrolyte, and then inject them into the prepared battery cell for in-situ curing.

[0177] After copolymerization of raw material A6 and raw material B6, a mixture of 4000 H atoms is formed. A6 Aggregation unit and 800 HB6 Polymer materials composed of polymer units, wherein the H in the structure of the polymer material A6 H B6 It is mainly arranged randomly.

[0178] Where H A6 The structure of the polymer unit is -Q1 is -CH3, -Q2 is m is 1, p is 4000.

[0179] H B6 The structure of the polymer unit is -Q3 is -CH3, -Q4 is n is 800.

[0180] Example 7

[0181] Raw material A7: Raw material B7:

[0182] Preparation method: Raw material A7 is an existing substance, CAS: 2429914-94-1. The 1H NMR spectrum of raw material A7 is shown below. 1 H NMR (300MHz, DMSO, δppm): 7.72(d, 2H), 7.40(d, 2H), 7.48(d, 1H), 4.51(d, 2H), 4.31(m , 2H), 4.19(m, 4H), 4.47(d, 2H), 1.36(t, 6H), 6.12(dd, 1H), 6.41(d, 1H), 5.83(d, 1H).

[0183] Raw material B7: First and The amidation reaction is carried out to obtain (For the specific synthetic route, see Nature Communications, 12(1), 930; 2021. DOI: 10.1038 / s41467-021-21190-8), and then bromine was obtained at the benzylic position using the NBS radical reaction. (For the specific synthetic route, see Malaria Journal, 13, 190 / 1-190 / 26, 26; 2014. DOI: 10.1186 / 1475-2875-13-190). Then, α-hydroxyl groups of sulfonyl lactone sulfur are dehydrogenated with n-butyllithium, followed by nucleophilic substitution with a substrate of benzyl bromide to obtain starting material B7 (for the specific synthetic route, see Chemical Communications, 47(41), 11465-11467; 2011. DOI: 10.1039 / c1cc14435a.). The 1H NMR spectrum of starting material B7... 1HNMR (300MHz, DMSO, δδSOM): 9.54 (s, 1H), 3.57 (m, 1H), 4.32 (m, 1H), 4.22 (m, 1H), 2.50 (m, 1H), 2.25 ( m, 1H), 7.69 (d, 2H), 7.17 (d, 2H), 2.94 (dd, 1H), 2.69 (dd, 1H), 1.98 (s, 3H), 5.79 (s, 1H), 5.72 (s, 1H).

[0184] Application method: Raw materials A7 and B7 are pre-placed in the positive electrode slurry, mixed evenly, and then coated onto aluminum foil. The initiator solution is added to the electrolyte and then injected into the prepared battery cell. The mixture is solidified in situ at 50°C for 6 hours to form a positive electrode sheet with battery materials.

[0185] After copolymerization of raw material A7 and raw material B7, a mixture of 1000 H atoms is formed. A7 Aggregation unit and 360 H B7 Polymer materials composed of polymer units, wherein the H in the structure of the polymer material A7 H B7 It is mainly arranged randomly.

[0186] Where H A7 The structure of the polymer unit is -Q1 means none, -Q2 means none. m is 1, p is 1000.

[0187] H B7 The structure of the polymer unit is -Q3 is -CH3, -Q4 is n is 360.

[0188] Example 8

[0189] Raw material A8: Raw material B8:

[0190] Preparation method: Raw material A8 is an existing substance, CAS number 2230541-46-3. MS (ESI) m / z 286.08 (MH) + .

[0191] Raw material B8:

[0192] The first step involves dehydrogenating the sulfonyl lactone with n-butyllithium, followed by nucleophilic addition with cyclohexanone, and hydrolysis to yield the alcohol. The second step involves esterification with acrylic acid to obtain raw material B8. (Ref 1: Journal of Organic Chemistry, 46(1), 101-6; 1981. DOI: 10.1021 / jo00314a022), Ref 2: Azerbaidzhanskii Khimicheskii Zhurna l, (2), 131-134; 2009). MS (ESI) m / z 274.09 (MH) + .

[0193] Application method: Raw materials A8 and B8 are prepared into a precursor liquid and coated on the surface of the positive electrode, and cured in situ to form a positive electrode with the polymer material coating.

[0194] After copolymerization of raw material A8 and raw material B8, a mixture of 500 H atoms is formed. A8 Aggregation unit and 400 H B8 Polymer materials composed of polymer units, wherein the H in the structure of the polymer material A8 H B8 Mainly based on two H A8 A polymer unit H B8 The aggregation units are arranged in an alternating manner.

[0195] Where H A8 The structure of the polymer unit is -Q1 means none, -Q2 means none. m is 1, p is 500.

[0196] H B8 The structure of the polymer unit is -Q3 means none, -Q4 means none. n is 400.

[0197] Example 9

[0198] Raw material A9: MS(ESI) m / z 305.06(MH) +

[0199] Raw material B9: MS(ESI) m / z 194.03(MH) + Raw material B9 is an existing substance, CA S: 63411-25-6

[0200] Preparation method of raw material A9:

[0201] The intermediate is obtained by esterification and hydrolysis of glutaric anhydride and vinyl alcohol. The pyridine phosphoric acid was then prepared into lithium alcohol, which was then esterified with an equivalent amount of the previously prepared intermediate to form raw material A9. (Ref: Zhurnal Obshchei Khimii, 65(11), 1924-5; 1995).

[0202] Application method: Raw materials A9 and B9 are prepared into a precursor liquid and coated on the surface of the negative electrode, and then cured in situ to form a negative electrode with the polymer material coating.

[0203] After copolymerization of raw material A9 and raw material B9, a mixture of 8000 H atoms is formed. A9 Aggregation unit and 640 H B9 Polymer materials composed of polymer units, wherein the H in the structure of the polymer material A9 H B9 It is mainly arranged randomly.

[0204] Where H A9 The structure of the polymer unit is -Q1 means none, -Q2 means none. m is 1, p is 8000.

[0205] H B9 The structure of the polymer unit is -Q3 means none, -Q4 means none. n is 640.

[0206] Example 10

[0207] Raw material A10: MS(ESI) m / z 334.11(MH) + (Raw material A10 is an existing substance, CAS: 2542065-61-0)

[0208] Raw material B10: MS(ESI) m / z 190.11(MH) + (Raw material B10 is an existing substance, CAS: 35836-29-4)

[0209] Application method: Add raw materials A10, B10 and initiator to the electrolyte to prepare a precursor solution, and then inject the precursor solution into the battery cell for in-situ curing.

[0210] After copolymerization, raw material A10 and raw material B10 form a group consisting of 10 H atoms. A10 Aggregation unit and 9 H B10 Polymer materials composed of polymer units, wherein the H in the structure of the polymer material A10 H B10 It is mainly arranged randomly.

[0211] Where H A10The structure of the polymer unit is -Q1 is -Q2 is m is 1, p is 10.

[0212] H B10 The structure of the polymer unit is -Q3 means none, -Q4 means none. n is 9.

[0213] Example 11

[0214] Raw material A11: MS(ESI) m / z 705.25(MH) + (A11 is an existing substance, CAS: 68397-51-3)

[0215] Raw material B11: MS(ESI) m / z 187.08(MH) +

[0216] Preparation method of raw material B11: Obtained through hydrolysis Obtained by oxidation with manganese dioxide (DCM, 80% oxygen) The preparation was obtained by coupling reaction of CuCN with bromoalkane.

[0217] The reaction was prepared by Br2 addition followed by substitution with NaF. Under nitrogen protection, 0.2 mmol of NaF was added to a 25 mL reaction tube. 2 mL of dry dichloromethane was cooled to 0°C, and 0.2 mmol of liquid bromine was added dropwise. After the addition was complete, the reaction was allowed to proceed at room temperature for 1 h. 1 mL of saturated sodium thiosulfate aqueous solution was added until colorless. 2 mL of water was added, and the mixture was extracted with dichloromethane. The organic phases were combined, washed with saturated NaCl, dried over anhydrous sodium sulfate, and distilled under reduced pressure to obtain the crude product. This crude product was added to a 25 mL reaction tube, along with 2 mL of dry dichloromethane, 0.1 mmol of benzyltriethylammonium chloride (TEBAC), and 0.2 mmol of NaF. The reaction was stirred at 40°C for 8 h, cooled to room temperature, quenched with water, extracted with dichloromethane, and the organic phases were combined, dried, and distilled under reduced pressure to obtain the crude product. The crude product.

[0218] Hydrolysis occurs under alkaline conditions. Under nitrogen protection, [the process continues]. The crude product was added to a 25 mL reaction tube, followed by 2 mL of 1,4-dioxane and 100 μL of 3M NaOH. The mixture was heated to 90 °C and reacted for 8 h. After cooling to room temperature, 5 mL of water was added, and the mixture was extracted with 3 × 5 mL of dichloromethane. The organic phases were combined, washed with saturated NaCl, dried over anhydrous sodium sulfate, filtered, distilled under reduced pressure, and subjected to column chromatography to obtain the final product.

[0219] Dehydration condensation under acetic anhydride conditions. Under nitrogen protection, 0.2 mmol of... Add to a 25 mL reaction tube, add 1 mL of acetic anhydride, heat to 120 °C and react for 8 h, cool and then distill under reduced pressure, and purify by column chromatography to obtain

[0220] The n-butyllithium was prepared by low-temperature hydrogen dehydrogenation and nucleophilic substitution. Under nitrogen protection, 0.2 mmol of... Add to a 25 mL Schlenk reaction tube, add 2 mL of dry tetrahydrofuran, cool to -78 °C, add n-butyllithium dropwise, after the addition is complete, react for 1 h, add bromoisopentene dropwise, react for 1 h, return to room temperature and react for 1 h, quench with water, add 5 mL of water, extract with 3 × 5 mL dichloromethane, combine the organic phases, wash the organic phase with saturated NaCl, dry with anhydrous sodium sulfate, filter, distill under reduced pressure, and column chromatography to obtain the starting material B11.

[0221] Application method: Raw materials A11 and B11 are prepared into a precursor liquid and coated on the surface of the diaphragm. The diaphragm is then cured in situ to form a diaphragm with the polymer material coating.

[0222] After copolymerization of raw material A11 and raw material B11, a copolymer is formed with 100 H atoms. A11 Aggregation unit and 75 H B11 Polymer materials composed of polymer units, wherein the H in the structure of the polymer material A11 H B11 It is mainly a block arrangement.

[0223] Where H A11 The structure of the polymer unit is -Q1 is -CH3, -Q2 is m is 1, p is 100.

[0224] H B11 The structure of the polymer unit is -Q3 is -CH3, -Q4 is n is 75.

[0225] Example 12

[0226] Raw material A12: MS(ESI) m / z 334.11(MH) + (Raw material A12 is an existing substance, CAS: 936752-22-6)

[0227] Raw material B12: B12 is an existing substance, CAS: 1686096-69-4, MS (ESI) m / z 189.98 (MH). +

[0228] Application method: Add raw materials A12, B12 and initiator to the electrolyte to prepare a precursor solution, and then inject the precursor solution into the battery cell for in-situ curing.

[0229] After copolymerization of raw material A12 and raw material B12, a mixture of 600 H atoms is formed. A12 Aggregation unit and 360 H B12 Polymer materials composed of polymer units, wherein the H in the structure of the polymer material A12 H B12 It is mainly a block arrangement.

[0230] Where H A12 The structure of the polymer unit is -Q1 is -Q2 is m is 1, p is 600.

[0231] H B12 The structure of the polymer unit is -Q3 is -O-CH3, -Q4 is... n is 360.

[0232] Example 13

[0233] Battery material G1: MS(ESI) m / z 3272.54 (MH) +

[0234] Application method: First, polymer material G1 is prepared, then polymer material G1 is mixed into the negative electrode slurry and coated onto copper foil to obtain a negative electrode containing polymer material G1. The positive electrode, negative electrode and separator are stacked and baked to obtain a dry cell. Then, electrolyte is injected, the battery is encapsulated, and left to stand at room temperature for 12 hours to allow the cell to be fully wetted, thus obtaining a solid-state battery containing polymer material G1.

[0235] Example 14

[0236] Battery material G2: MS(ESI) m / z 4132.98(MH) +

[0237] Application method: First, polymer material G2 is prepared, and then polymer material G2 is added to electrolyte to dissolve it to obtain electrolyte containing battery material. Then, the positive electrode, negative electrode and separator are stacked and baked to obtain dry cell. After the electrolyte is injected into the cell, the battery is packaged and left to stand at room temperature for 12 hours to allow the cell to be fully wetted, thus obtaining solid-state battery containing polymer material G2.

[0238] Example 15

[0239] Battery material G3:

[0240] Application method: First, polymer material G3 is prepared, then polymer material G3 is mixed into the negative electrode slurry and coated onto copper foil to obtain a negative electrode containing polymer material G3. The positive electrode, negative electrode and separator are stacked and baked to obtain a dry cell. Then, electrolyte is injected, the battery is encapsulated, and left to stand at room temperature for 12 hours to allow the cell to be fully wetted, thus obtaining a solid-state battery containing polymer material G3.

[0241] Example 16

[0242] Battery material G4:

[0243] Application method: First, polymer material G4 is prepared, then polymer material G4 is added to electrolyte to dissolve and obtain electrolyte containing battery material. Then, positive electrode, negative electrode and separator are stacked and baked to obtain dry cell. After electrolyte is injected into cell, the battery is packaged and left to stand at room temperature for 12 hours to allow cell to be fully wetted, thus obtaining solid battery containing polymer material G4.

[0244] Experimental Example 1

[0245] I. Preparation of the positive electrode sheet

[0246] The positive electrode active material, conductive agent, binder, and fast ion conductor were mixed uniformly according to the proportions listed in Table 1C1-C6 to obtain a positive electrode slurry with a certain degree of fluidity; then, it was coated onto aluminum foil, controlling the areal capacity of the positive electrode sheet to be 4.5 mAh / cm². 2 The cathode sheets were dried by forced air and rolled to obtain positive electrode sheets named C1, C2, ... C6. The conductive agent consisted of carbon nanotubes and conductive carbon black (CNT+Super-P, with a mass ratio of 1:2), and the binder was polyvinylidene fluoride (PVDF). The stated ratio represents the mass ratio of the cathode material, binder, conductive agent, and fast ion conductor.

[0247] The cathode material is LiCoO2 (abbreviated as LCO) or LiNi. 0.83 Co 0.12 Mn 0.05 O2 (abbreviated as Ni83), LiNi 0.8 Co 0.15 Al 0.05 O2 (abbreviated as NCA). The fast ion conductor is Li. 1.4 Al 0.4 Ti 1.6 (PO4)3 (abbreviated as LATP), Li 6.4 La3Zr 1.6 Ta 0.6 O 12(abbreviated as LLZO).

[0248] Table 1 Positive electrode sheet

[0249]

[0250]

[0251] II. Preparation of the negative electrode sheet

[0252] The active material, conductive agent, and binder of the negative electrode main material were added to deionized water according to the data listed in Table 2 and mixed evenly to obtain a negative electrode slurry with a certain fluidity. Then, it was coated on copper foil, and the areal capacity of the positive electrode sheet was controlled to be 4.8 mAh / cm². 2 The material is dried by blowing air and rolled to obtain a negative electrode sheet, or lithium metal is used directly as the negative electrode, and named F1, F2, ... F4 respectively. The ratio is the mass ratio of the negative electrode main material, binder, and conductive agent.

[0253] Table 2 Negative Electrode Sheets

[0254] Number Negative electrode Conductive agent Binder Proportion F1 Silicon-oxygen-carbon CNT + Super-P CMC + SBR 95:2:3 F2 Natural graphite CNT + Super-P CMC + SBR 95:2:3 F3 Silicon-carbon CNT + Super-P CMC + SBR 95:2:3 F4 Metallic lithium —— —— ——

[0255] The silicon-carbon material used is SL450A-SOC nano silicon-carbon anode material from Liyang Tianmu Pioneer Battery Materials Technology Co., Ltd., and the silicon-oxygen-carbon material is S450-2A silicon-oxygen-carbon anode material from BTR New Energy Materials Co., Ltd.; the binder is sodium carboxymethyl cellulose and styrene-butadiene rubber (CMC+SBR).

[0256] III. Diaphragm

[0257] Table 3 Diaphragms

[0258] Number Separator Specification / grid S1 PP double-sided ceramic 2 + 12 + 2 (12 - base 2 - aluminum oxide ceramic) S2 PE double-sided ceramic 2 + 12 + 2 (12 - base 2 - aluminum oxide ceramic)

[0259] IV. Electrolyte

[0260] In practical applications, the electrolyte can be a commercially available electrolyte for lithium secondary batteries, or it can be formulated independently. The present invention does not have any particular limitations on its composition and ratio.

[0261] Table 4 Electrolyte Preparation

[0262]

[0263] V. Battery Assembly

[0264] Preparation of batteries 1-4, 10, 12, control batteries 1-4, control batteries 7-13, and control batteries 16-18

[0265] According to the data listed in Table 5, in an environment with a dew point below -45°C, the precursor solution is injected into the cell and left to stand for 6-12 hours, then cured at 50-60°C for 6-8 hours to obtain an electrolyte that has been polymerized in situ. Then, the battery prepared by in-situ curing is obtained through processes such as formation, secondary sealing, and capacity testing.

[0266] Preparation of Battery 5 and Comparative Battery 5

[0267] Raw material A5 is pre-placed in the positive electrode sheet. First, raw material A5 is added to the slurry of positive electrode C3 and mixed evenly. It is then coated onto aluminum foil to obtain a positive electrode sheet containing raw material A5. The positive electrode sheet, negative electrode sheet and separator are stacked and baked to obtain a dry cell. Then, B5 and initiator are added to the electrolyte and injected into the prepared cell for in-situ curing to obtain a solid-state battery containing battery materials.

[0268] Preparation of Battery 6 and Comparative Battery 6

[0269] Raw material A6 is pre-placed on the separator. First, raw material A6 is prepared into a slurry and coated on the surface of the separator, with the coating thickness controlled to be 3 mm. The positive electrode, negative electrode, and separator containing raw material A6 are stacked and baked to obtain a dry cell. Then, B6 and an initiator or an initiator alone are added to the electrolyte and injected into the prepared cell for in-situ curing to obtain a solid-state battery containing polymer materials.

[0270] Preparation of Battery 7

[0271] According to the data listed in Table 5, raw materials A7 and B7 (the molar ratio of B7 to A7 is 0.36) are mixed into the slurry for preparing the positive electrode C4 and mixed evenly. The mixture is then coated onto aluminum foil to obtain a positive electrode with pre-placed raw materials A7 and B7. The initiator AIBN is added to the electrolyte E7. The above positive electrode sheet, negative electrode sheet F2 and separator S2 are stacked and baked to obtain a dry cell. The electrolyte with added initiator is then injected, the battery is encapsulated, and the cell is left to stand at room temperature for 12 hours to allow it to be fully impregnated, thus obtaining a solid-state battery containing battery materials.

[0272] Preparation of Battery 8

[0273] According to the data listed in Table 5, raw materials A8, B8 (molar ratio of B8 to A8 is 0.8) and initiator BPO were added to the solvent and mixed evenly to obtain a raw material solution containing polymer material. This solution was coated onto the surface of the positive electrode C5, and the coating thickness was controlled to be 2 μm. In situ polymerization of monomers was initiated at 50°C to obtain a positive electrode sheet containing polymer material coating. The positive electrode sheet containing polymer material coating, the negative electrode sheet F1 and the separator S1 were stacked and baked to obtain a dry cell. Electrolyte E4 was then injected, the battery was encapsulated, and the cell was allowed to stand at room temperature for 12 hours to fully impregnate it, thus obtaining a solid-state battery containing battery material.

[0274] Preparation of Battery 9

[0275] According to the data listed in Table 5, raw materials A9, B9 (the molar ratio of B9 to A9 is 0.08) and initiator BPO were added to the solvent and mixed evenly to obtain a raw material solution containing polymer material. This solution was coated onto the surface of the negative electrode F1, and the coating thickness was controlled to be 2 μm. Then, in-situ polymerization of monomers was initiated at 50°C to obtain a negative electrode sheet containing polymer material coating. The positive electrode sheet C6, the above-mentioned negative electrode sheet containing polymer material coating and the separator S1 were stacked and baked to obtain a dry cell. Then, electrolyte E5 was injected, the battery was encapsulated, and the cell was left to stand at room temperature for 12 hours to fully impregnate it, thus obtaining a solid-state battery containing battery material.

[0276] Preparation of battery 11

[0277] According to the data listed in Table 5, raw materials A11, B11 (molar ratio of B11 to A11 is 0.75) and initiator BPO were added to the solvent and mixed evenly to obtain a raw material solution containing polymer material. This solution was coated onto the surface of separator S2, and the coating thickness was controlled to be 2 μm. Then, in-situ polymerization of monomers was initiated at 50°C to obtain a separator containing polymer material coating. The positive electrode C5, negative electrode F4 and the above-mentioned separator containing polymer material coating were stacked and baked to obtain a dry cell. Then, electrolyte E6 was injected, the battery was encapsulated, and left to stand at room temperature for 12 hours to allow the cell to be fully wetted, thus obtaining a solid-state battery containing battery material.

[0278] Preparation of batteries 13 and 15

[0279] First, a polymer material is prepared. Then, the polymer material is mixed into the slurry for preparing the negative electrode F1 and mixed evenly. The mixture is then coated onto an aluminum foil to obtain a positive electrode containing the polymer material. The positive electrode C2 containing the polymer material, the negative electrode C2 containing the polymer material, and the separator S1 are stacked and baked to obtain a dry cell. Then, an electrolyte E2 containing battery material is injected, the battery is encapsulated, and the cell is left to stand at room temperature for 12 hours to allow it to be fully wetted, thus obtaining a solid-state battery containing the polymer material.

[0280] Preparation of batteries 14 and 16

[0281] First, a polymer material is prepared, and then the polymer material is added to electrolyte E3 to dissolve it, thereby obtaining electrolyte E3 containing battery material. Then, the positive electrode, negative electrode and separator are stacked and baked to obtain a dry cell. The dry cell is injected with electrolyte containing battery material, the battery is encapsulated, and left to stand at room temperature for 12 hours to allow the cell to be fully wetted, thereby obtaining a solid-state battery containing polymer material G.

[0282] Comparison of the fabrication of batteries 14 and 15

[0283] According to the data listed in Table 5, in an environment with a dew point below -45°C, raw material A1 / A1+B1 is added to electrolyte E1. The positive electrode, negative electrode and separator are then stacked and baked to obtain a dry cell. The above electrolyte is injected, the battery is packaged, and it is left to stand at room temperature for 12 hours to allow the cell to be fully wetted, resulting in a battery containing raw material A1 / A1+B1 but without polymerization.

[0284] The amount of initiator added to the battery is 0.2% to 2% of the mass of raw materials A and B.

[0285] Table 5. Battery configuration and testing methods in the examples.

[0286]

[0287]

[0288] The structure of D1 is as follows: The structure of D2 is:

[0289] The structure of K1 is as follows: The structure of K2 is as follows:

[0290] The structure of K3 is as follows:

[0291] VII. Battery Testing

[0292] After the secondary battery was completely cured in situ, the first-cycle discharge capacity, first-cycle efficiency, and capacity retention rate after 200 cycles were tested at room temperature. The test voltage range was 2.75 to 4.2V, and the cycling mode was 0.5C / 0.5C 200 cycles (C represents the rate). The test results are shown in Table 6.

[0293] Table 6 Battery Test Results

[0294]

[0295]

[0296] This invention provides a polymer material containing phosphorus groups, which, when used to prepare batteries by in-situ or non-in-situ curing methods, greatly improves the cycle stability and safety of the batteries and extends their service life.

[0297] As can be seen from Table 6, in the battery system with high-nickel ternary (Ni83, NCA) and lithium cobalt oxide as the positive electrode and graphite, silicon-carbon, silicon-oxygen-carbon, and lithium metal as the negative electrode, the energy density of the battery prepared by this invention is only slightly reduced compared to conventional lithium batteries, but the cycle stability of the battery is significantly improved.

[0298] Batteries prepared using polymers generated from raw materials A and B (batteries 1-12, 14, and 16) have capacities ranging from 10.25 Ah to 10.68 Ah and a capacity retention rate of 92.76% to 94.11% after 200 cycles. Batteries prepared using polymers generated from raw material A alone (comparison batteries 1-8, 13, and 15) have capacities ranging from 9.88 to 10.16 Ah and a capacity retention rate of 90.57% to 91.88% after 200 cycles. The capacity retention rates of batteries 1-12, 14, and 16 after 200 cycles are higher than those of comparison batteries 1-8, 13, and 15, indicating that batteries prepared by simultaneously introducing polymers generated from raw materials A and B have higher cycle stability. Batteries made using only polymers derived from raw material B (comparative batteries 9-11) have capacities between 9.72 and 9.74 Ah and a capacity retention rate of 92.46% to 92.54% after 200 cycles. The capacity retention rate of comparative batteries 9-11 after 200 cycles is higher than that of comparative batteries 1-8, 13, and 15, indicating that the introduction of B in this invention can improve the cycle stability of the battery. The batteries prepared using only raw material D (comparison batteries 12-13) had capacities between 9.12 and 9.22 Ah, with a capacity retention of 79.87% to 79.96% after 200 cycles. The batteries prepared using raw materials A or A+B without in-situ curing (comparison batteries 14-15) had capacities between 9.57 and 9.63 Ah, with a capacity retention of 89.77% to 89.93% after 200 cycles. In contrast, the blank batteries 1-5 had capacities between 9.65 and 9.78 Ah, with a capacity retention of 84.19% to 86.91% after 200 cycles.

[0299] In comparison battery 1, the raw material A contains an ester group between P and the double bond; in comparison batteries 7-8, the raw material A does not contain an ester group between P and the double bond. Comparing the electrochemical performance of batteries 1 and 7-8 in terms of initial efficiency and capacity retention, it can be seen that the presence of an ester group between P and the double bond in the structure of raw material A results in better electrochemical performance. In comparison batteries 16-17, the substituents connected to the P atom in raw materials K1 and K2 do not contain ring structures; in batteries 1-16 and comparison batteries 1-8, the substituents connected to the P atom in raw material A all contain at least one ring structure. Comparing the electrochemical performance of these batteries in terms of initial efficiency and capacity retention, it can be seen that the batteries with ring structures in the substituents connected to P in raw material A exhibit better electrochemical performance.

[0300] Depend on Figure 1 It can be seen that the capacity retention rate of battery 1 is much higher than that of the control battery 12 and the blank battery 1, indicating that the polymer material provided in this application can significantly improve the electrochemical performance of the battery when applied in the battery.

[0301] Battery 1 exhibits a higher capacity retention rate than control battery 1, indicating that the battery prepared by introducing the polymer generated from raw materials A and B simultaneously has better cycle performance than the battery prepared by the polymer generated from raw material A alone. Battery 14 exhibits a slightly lower capacity retention rate than battery 1, indicating that the battery prepared using in-situ curing has superior electrochemical performance. This is because the in-situ curing method significantly improves the interfacial contact between the electrolyte and the electrode, reducing polarization and interfacial impedance, thus achieving better electrical performance (such as energy density utilization, first-cycle efficiency, and capacity retention). As can be seen from batteries 1-14, this invention is applicable to various applications. Raw materials can be directly applied to the electrolyte, pre-placed in the battery assembly, prepared as a precursor solution and coated onto the electrode and separator surfaces, or first prepared into a polymer material and then applied to the battery. The application methods shown in the above embodiments are only preferred application methods for the specific raw material / battery material; other in-situ curing or non-in-situ curing application methods are also applicable.

[0302] Experimental Example 2

[0303] Battery safety performance test

[0304] The prepared batteries 1-16, control batteries 1-18, and blank batteries 1-5 were subjected to nail penetration safety tests in accordance with the safety requirements and test methods for power batteries for electric vehicles in the lithium-ion battery GB-T31485-2015 standard.

[0305] I. Needle Penetration Test: The battery is charged at a constant current and constant voltage of 1C, with a cutoff current of 0.05C. A φ8mm high-temperature resistant steel needle is used to penetrate the battery from a direction perpendicular to the battery plates at a speed of 25mm / s. The penetration position should be close to the geometric center of the pierced surface. The steel needle remains in the battery. Observe for 1 hour and monitor the change in the surface temperature of the cell during the process. Record whether the cell catches fire or explodes. The results are shown in Table 7.

[0306] Table 7 Record of Cell Needle Puncture Results

[0307]

[0308]

[0309] This invention provides a polymer material containing phosphorus groups. By introducing a polymer material containing phosphorus groups into a battery through in-situ curing or non-in-situ curing methods, the safety of the battery is greatly improved.

[0310] As shown in Table 7, lithium batteries (batteries 1-12, 14, and 16) prepared using polymers generated from raw materials A and B did not catch fire or explode during the nail penetration test, and the cell surface temperature during the nail penetration test was 26.0–34.6℃, thus improving battery safety. In contrast, batteries prepared using polymers generated from raw material A only (comparison batteries 1-8, 13, and 15) also did not catch fire or explode during the nail penetration test, and the cell surface temperature during the nail penetration test was 40.1–49.4℃. The cell surface temperatures of batteries 1-12, 14, and 16 were slightly lower than those of comparison batteries 1-8, 13, and 15, indicating that batteries prepared by simultaneously introducing polymers generated from raw materials A and B have higher safety. Batteries made using only polymers from raw material B (comparison batteries 9-11) caught fire and exploded upon needle penetration, with cell surface temperatures ranging from 295.2 to 299.1°C. Batteries made using only raw material D (comparison batteries 12-13) caught fire and exploded upon needle penetration, with cell surface temperatures ranging from 602.4 to 619.3°C. Batteries made using raw materials A or A+B without in-situ curing (comparison batteries 14-15) caught fire and exploded upon needle penetration, with cell surface temperatures ranging from 495.8 to 497.7°C. Blank batteries 1-5 caught fire and exploded upon needle penetration, with cell surface temperatures ranging from 615.3 to 635.0°C.

[0311] In contrast, the raw material A used in battery 1 contains ester groups between P and the double bond, and the surface temperature of the battery cell after needle puncture is 40.6℃. In contrast, the raw material A used in batteries 7-8 does not contain ester groups between P and the double bond, and the surface temperatures of the battery cells after needle puncture are 49.4℃ and 48.7℃ respectively, higher than that of battery 1. This indicates that the presence of ester groups between P and the double bond in raw material A is beneficial for further improving battery safety. In batteries 1-16 and batteries 1-8, the substituents directly connected to the P atom in raw material A all contain cyclic structures, and the surface temperature of the battery cells after needle puncture is... The surface temperature ranged from 26.0 to 49.4℃. In contrast, the substituents directly bonded to the P atom in raw materials K1 and K2 used in batteries 16-17 did not contain cyclic structures. The surface temperatures of these batteries after needle penetration were 79.3℃ and 78.9℃, respectively. This indicates that although the introduction of K1 or K2 improved battery safety to some extent, an internal short circuit still occurred during needle penetration, resulting in a heating rate greater than the heat dissipation rate. This suggests that K1 or K2 was insufficient in suppressing battery heating. Furthermore, it indicates that the cyclic structure in the substituents directly bonded to the P atom in raw material A provides the battery with higher safety.

[0312] from Figure 2It can be seen more intuitively that the battery prepared by the polymer generated from raw material A or the polymer generated by simultaneously introducing raw material A+B still maintains good performance after being punctured, while the blank battery and the control battery caught fire and exploded after 12 puncture tests, and suffered severe damage. This shows that the polymer material provided in this application can significantly improve the safety performance of the battery when applied to the battery.

[0313] II. Cell Thermal Shock Safety Test

[0314] The battery was charged at 1C constant current and constant voltage with a cutoff current of 0.05C; heated to 180℃ for 2 hours: heating rate 5℃ / s, heated to 180℃ and held for 2 hours, observed for 1 hour; and recorded whether the battery caught fire or exploded. "No fire or explosion" was considered a pass, otherwise it was a failure. The change in the surface temperature of the battery cell was monitored during the process. The test results are shown in Table 8.

[0315] Table 8 Record of Cell Thermal Shock Safety Results

[0316]

[0317]

[0318] This invention provides a polymer material containing phosphorus groups. By introducing a polymer material containing phosphorus groups into a battery through in-situ curing or non-in-situ curing methods, the safety of the battery is greatly improved.

[0319] As shown in Table 8, all batteries prepared using polymers generated from raw material A or polymers generated by simultaneously introducing raw materials A and B passed the thermal shock test. Batteries prepared using polymers generated from raw material B, batteries containing raw material A or both raw materials A and B but without polymerization, batteries containing only D1 and D2, and blank batteries failed the thermal shock test. This further demonstrates that the present invention improves battery safety.

[0320] This application introduces a polymer material containing phosphorus groups, which significantly improves battery safety when used to prepare batteries via in-situ or non-in-situ curing methods. Furthermore, batteries prepared using in-situ curing exhibit superior electrochemical performance because the method greatly improves the interfacial contact between the electrolyte and the electrode, reducing polarization and interfacial impedance, thus resulting in better electrical performance.

[0321] (3) Compression test: After fully charging the battery, place it in two planes and compress it perpendicular to the plate direction at a rate of 2 mm / s. Stop compressing when the voltage reaches 0V or the battery deformation reaches 50%. The battery passes the test if it does not catch fire or explode during the compression process.

[0322] Table 9 Comparison of compression test results

[0323]

[0324]

[0325] This invention provides a polymer material containing phosphorus groups. By introducing a polymer material containing phosphorus groups into a battery through in-situ curing or non-in-situ curing methods, the safety of the battery is greatly improved.

[0326] As shown in Table 9, all batteries prepared using polymers generated from raw material A or polymers generated by simultaneously introducing raw materials A and B passed the extrusion test. Batteries prepared using polymers generated from raw material B, batteries containing raw material A or both raw materials A and B but without polymerization, batteries containing only D1 and D2, and blank batteries failed the extrusion test. This further demonstrates that the present invention improves battery safety.

[0327] This application introduces a polymer material containing phosphorus groups, which significantly improves battery safety when used to prepare batteries via in-situ or non-in-situ curing methods. Furthermore, batteries prepared using in-situ curing exhibit superior electrochemical performance because the method greatly improves the interfacial contact between the electrolyte and the electrode, reducing polarization and interfacial impedance, thus resulting in better electrical performance.

[0328] In the nail penetration test, thermal shock safety test, and extrusion test, all batteries prepared using polymers derived from raw material A or polymers derived from both raw materials A and B passed the extrusion test. Batteries prepared using polymers derived from both raw materials A and B exhibited better safety and electrochemical performance. Batteries prepared using polymers derived only from raw material B, batteries containing only D1 and D2, and blank batteries all failed the safety tests. This demonstrates that the polymer material described in this application, when used in batteries, can significantly improve battery safety performance.

[0329] It should be noted that raw material A, or a mixture of raw material A and raw material B, in this patent can also be directly used with commercial electrolytes and still achieve excellent results, indicating that the raw materials used to prepare polymer materials in this application have good compatibility with various electrolytes.

[0330] The raw materials for which preparation methods are not described in the embodiments are all existing raw materials that can be purchased directly; the raw materials for which preparation methods are described are all existing technologies, and the raw material preparation methods are not within the protection scope of this application, so they are not described in detail in the specification.

[0331] In summary, the battery prepared using this invention can not only significantly improve battery safety performance, but also maintain excellent electrochemical performance, making it suitable for large-scale promotion and application.

[0332] In this invention, only some structures were selected as representatives in the embodiments to illustrate the preparation method and effects of this application, and other unlisted structures have similar effects.

[0333] For example, the polymeric units [M1-M2] constituting polymeric material G may also include: Furthermore, the polymeric units represented by R5 and / or R6 constituting polymeric material G may also include: Due to space limitations, other polymeric units can be deduced similarly and will not be listed here one by one. All polymeric material structures formed by any combination of the above polymeric units are within the scope of protection of this application.

[0334] In the above structure, R can be H, Li, or BF3Li, and A indicates that any position on the ring can be substituted by a halogen atom, alkyl group, or other substituents, especially F. The values ​​of m, p, and n can be found in the invention description section. The terminal groups in the above structure can be any group, and this application does not impose any restrictions on them.

[0335] Polymer material structures can be obtained by combining any one, two or more of the above-mentioned polymer units in a block, alternating or random arrangement, and these polymer material structures are all within the scope of protection of this application.

[0336] In this invention, only some structures were selected as representatives in the embodiments to illustrate the preparation method and effects of this application, and other unlisted structures have similar effects.

[0337] It should also be noted that the applicant has conducted a great deal of experiments on this series of structures. Sometimes, in order to better compare with existing systems, the same structure and system have been tested more than once. Therefore, there may be some errors between different tests.

[0338] Finally, it should be noted that the above-described embodiments are only used to illustrate the technical solutions of the present invention, and are not intended to limit them. Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some or all of the technical features therein. Such modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of the present invention.

[0339] Unless otherwise stated, the numerical ranges in this document include not only the entire range within its two endpoints, but also the subranges contained therein.

[0340] The preferred embodiments and examples of this application have been described in detail above with reference to the accompanying drawings. However, this application is not limited to the above embodiments and examples. Within the scope of knowledge possessed by those skilled in the art, various changes can be made without departing from the concept of this application.

Claims

1. A polymer material for lithium batteries, characterized in that, The polymer material has a structure comprising at least [M1-M2] polymer units as shown in Formula 1: Formula 1; Furthermore, the structure of the polymer material is selected from: or ; Among them, M1 is selected from C, N, P, S, Si, and M2 is selected from C, O, N, P, S, Si; R1-R4 are independently selected from any one of chains or rings that are unsubstituent, contain substituents, or do not contain substituents. When R1 is selected from a chain that contains substituents or does not contain substituents, the chain is a pure carbon chain or a carbon chain containing only one heteroatom. R1 contains at least one unsaturated bond and / or at least one heteroatom, wherein the heteroatom includes N, O, P, S, Si, and F; the unsaturated bond is =O; R1 contains at least one ; where -O is directly connected to P or M1 or indirectly connected through a chain and / or ring, and -C=O is directly connected to P or M1 or indirectly connected through a chain and / or ring. R3-R4 are independently selected from any one of the following: none, saturated carbon chains consisting of 1-10 carbon atoms, or unsaturated carbon chains; R5-R6 are independently selected from any one of chains or rings with or without substituents, or polymeric units formed based on chains or rings. When R5 and / or R6 represent polymeric units, they are selected from -[M1-M2]- polymeric units or other polymeric units different from -[M1-M2]-. Indicates a ring structure; A1 indicates that the ring structure can be substituted at any position; m is selected from 0.01 to 1, indicating that there is one in every 1 / m -[M1-M2]-aggregation units. Connected to M1 or M2; p is an integer between 10 and 10000, representing the degree of aggregation of the -[M1-M2]- aggregation unit; M3 is selected from C, N, P, S, and Si; M4 is selected from C, O, N, P, S, and Si. R 10 -R 14 Independently selected from any one of chains or rings that are unsubstituted, contain substituents, or do not contain substituents; n is an integer between 5 and 1000, representing the degree of aggregation of the -[M3-M4]- aggregation unit; When the polymer material structure is unfolded, individual -[M1-M2]-polymer units and individual -[M3-M4]-polymer units are arranged in a block manner, an alternating manner, a periodic manner, a gradient manner, or a random manner; R 14 It is selected from a ring or chain containing at least one heteroatom, wherein any position of the ring or chain can be substituted by a substituent.

2. The polymer material as described in claim 1, characterized in that, R 14 It is selected from a ring or chain containing at least two heteroatoms, and the ring or chain contains at least one =O.

3. The polymer material as described in claim 2, characterized in that, R 14 Selected from: , , , , , , ; In this context, A1 and A2 indicate that atoms on the ring / chain can be substituted by substituents.

4. The polymer material as described in claim 1, characterized in that, R3 is selected from OR, where R is selected from any one of H, Li, halogen atoms, chains or rings with or without substituents; The chain or ring containing or without substituents is a chain or ring composed of 1-8 atoms; The substituent represented by A1 is replaced by one or more halogen atoms, and the chain contains at least one heteroatom.

5. The polymer material as described in claim 4, characterized in that, The OR is OLi.

6. The polymer material according to claim 4, characterized in that, The substituent represented by A1 is replaced by F.

7. The polymer material according to any one of claims 1-6, characterized in that, The The ring structure represented is selected from single rings or multiple rings. The single ring is selected from 3-12 saturated carbon rings, saturated heterocycles, unsaturated carbon rings or unsaturated heterocycles. The multiple rings are selected from fused rings, bridged rings, spiral rings or linked rings formed by combining any two of the single rings based on the single ring.

8. The polymer material as claimed in claim 7, characterized in that, The monocyclic ring is selected from five- or six-membered unsaturated carbon rings or unsaturated heterocyclic rings.

9. The polymer material as claimed in claim 8, characterized in that, The monocyclic ring is selected from five- to six-membered unsaturated heterocyclic rings.

10. The polymer material according to claim 1, characterized in that, When the polymer material structure is unfolded, individual -[M1-M2]-polymer units and individual -[M3-M4]-polymer units are arranged in a block manner, an alternating manner, a periodic manner, a gradient manner, or a random manner.

11. The polymer material according to claim 1, characterized in that, Let H1 represent a single -[M1-M2]-aggregation unit H2 represents a single -[M3-M4]-polymer unit. In polymer materials, the arrangement of H1 and H2 is selected from any one or a combination of the following: Arranged in a segmented manner: H1-H1- H1-H1-H1-H2-H2-H2- -H2-H2; Arranged in an alternating manner: one or more H1s and one or more H2s are arranged alternately in sequence; Arranged in a periodic manner: multiple periods are formed by one or more H1 and one or more H2, and the multiple periods are arranged in sequence; Arranged in a gradient manner: the composition of H1 and H2 gradually changes along the chain; Irregular arrangement: One or more H1s and one or more H2s are arranged in any alternating pattern.

12. The polymer material according to claim 1, characterized in that, In the structure of the polymer material, m is selected from 1, p is selected from an integer between 30 and 8000, n is selected from an integer between 10 and 800, and p > n.

13. The polymer material according to claim 1, characterized in that, The polymer material is prepared at least based on the reaction of raw material A, or at least based on the reaction of raw material A and raw material B; The structure of raw material A is as follows: The structure of raw material B is as follows: .

14. An electrolyte, characterized in that, The electrolyte contains the polymer material as described in any one of claims 1-13, or a raw material for preparing the polymer material as described in claim 13.

15. A lithium battery, characterized in that, The battery comprises any one or more of the following: the polymer material as described in any one of claims 1-13, the raw material for preparing the polymer material as described in claim 13, and the electrolyte as described in claim 14.

16. The lithium battery as described in claim 15, characterized in that, The lithium battery is a lithium-ion battery or a lithium metal battery.

17. The lithium battery as described in claim 15, characterized in that, The lithium battery is a liquid battery, a hybrid solid-liquid battery, or an all-solid-state battery.

18. The lithium battery according to claim 17, characterized in that, The lithium battery is an all-solid-state battery.

19. The application of a polymer material as described in any one of claims 1-13 in a battery, characterized in that, The polymer material is placed in the battery assembly of the battery, and the battery is prepared by a non-in-situ curing process; Alternatively, the raw materials used to prepare the polymer material may be placed in the battery assembly of the battery, and the battery may be prepared by in-situ curing process; The battery assembly includes electrodes, a separator, and an electrolyte membrane.

20. The application of a polymer material as described in any one of claims 1-13 in a battery, characterized in that, The polymer material is placed in the cell of the battery, and the battery is prepared by a non-in-situ curing process; Alternatively, the raw materials used to prepare the polymer material can be placed in the battery cell, and the battery can be prepared by in-situ curing.

21. The application as described in claim 19 or 20, characterized in that, The non-in-situ curing method of placing the polymer material in the battery includes: (1) Placing the polymer material in the cell of the battery, comprising: The polymer material is first dissolved in the electrolyte and then injected into the prepared battery cell; (2) Placing the polymer material in the battery assembly of the battery, comprising: The polymer material is dissolved in a solvent and then coated onto an electrode sheet, separator, or formed into a separate film to form an electrode sheet, separator, or electrolyte membrane with a polymer material coating; or the polymer material is mixed into positive and negative electrode slurries to form an electrode sheet containing polymer material. The method of placing the raw material in the battery for in-situ curing includes: (1) Placing the raw material in the cell of the battery, comprising: The raw materials and initiator are added to the electrolyte, and an integrated solid-state battery is formed by in-situ curing; or at least one of the raw materials is pre-placed in the battery assembly, the initiator and the remaining raw materials are added to the electrolyte, and then injected into the prepared battery cell, and an integrated solid-state battery is formed by in-situ curing. (2) Placing the raw material in the battery assembly of the battery, comprising: The raw materials are prepared into a precursor solution and coated onto an electrode sheet, diaphragm, or formed into a film on its own, and then cured in situ to form an electrode sheet, diaphragm, or electrolyte membrane with a polymer material coating.

22. The application as described in claim 21, characterized in that, When the raw materials include raw material A and raw material B, the molar ratio of raw material B to raw material A is 0.02 to 1, and the total mass of raw material A and raw material B accounts for 1% to 50% of the total mass of the precursor liquid.

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