CN115882056A - Polymer material for lithium battery - Google Patents
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- CN115882056A CN115882056A CN202111166287.1A CN202111166287A CN115882056A CN 115882056 A CN115882056 A CN 115882056A CN 202111166287 A CN202111166287 A CN 202111166287A CN 115882056 A CN115882056 A CN 115882056A
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Abstract
The present application provides a polymer material for a lithium battery. The structure of the polymer material at least comprises- [ M ] shown as formula 1 1 ‑M 2 ]-a polymerization unit. The polymer material containing the phosphorus group can be flexibly applied to a battery, and plays a role in improving the safety of the battery, improving the ion transmission of the battery, improving the cycling stability of the battery and prolonging the service life of the battery.
Description
Technical Field
The application relates to the technical field of batteries, in particular to a polymer material for a lithium battery.
Background
Lithium Ion Batteries (LIBs) have the advantages of high energy density, long cycle life, low self-discharge rate, no memory effect and the like, and have wide application prospects in the field of new energy electric automobiles. With the continuous development of science and technology, the requirements on the performance of the lithium-ion battery are higher and higher, and with the continuous improvement of the energy density of the battery, the safety problem is more and more prominent. The conventional LIBs mainly use liquid electrolytes containing a large amount of flammable organic carbonate solvents, which easily causes safety problems such as leakage of electrolytes, thermal runaway or explosion. The polymer solid electrolyte has the advantages of light weight, flexibility, easy processing and the like, can solve the safety problem brought by liquid electrolyte, but has a series of problems of low room-temperature ionic conductivity, large interface resistance and the like.
The Gel Polymer Electrolytes (GPEs) are formed by swelling polymer matrixes and plasticizers, so that the gel polymer electrolytes have high ionic conductivity, meanwhile, the polymer matrixes in the GPEs form a cross-linking structure by chemical bonds or physical acting force to play a skeleton supporting role, and the flowing solvent molecules are fixed in the polymer gel skeleton, so that the electrolytes are in a non-flowing semi-solid state as a whole, are easy to process and difficult to leak, and the safety of a battery is improved. Therefore, gel Polymer Electrolytes (GPEs) capable of balancing interfacial contact and ionic conductivity have received extensive attention and extensive research in recent years.
The plasticizers used for the gel polymer are basically commonly used liquid electrolytes or organic carbonate solvents. For example, CN108682863A discloses a lithium battery polymer gel electrolyte, in which epoxy oleate and dimethyl carbonate are used as plasticizers, and although excellent ionic conductivity can be achieved, a large amount of flammable carbonate plasticizers exist in a polymer matrix, so that a lithium battery constructed by using the above method still has potential risks of combustion and explosion, and thus it is difficult to completely solve the safety problem of a high energy density battery.
Disclosure of Invention
In view of the above, embodiments of the present application provide a polymer material for a lithium battery to solve technical defects in the prior art.
The application provides a polymer material for a lithium battery, and the structure of the polymer material at least comprises- [ M ] shown as a formula 1 1 -M 2 ]-a polymerization unit:
wherein M is 1 Selected from C, N, P, S, si, M 2 Selected from C, O, N, P, S, si.
R 1 -R 4 Independently selected from any one of a chain or a ring without, containing a substituent or not containing a substituent, in R 1 Selected from the group consisting of substituted or unsubstituted chains, which are pure carbon chains, or carbon chains containing only one heteroatom; "contains only one heteroatom" means that one or more heteroatoms may be included in the chain, but all heteroatoms included in the chain are of the same kind, e.g. 1 or more oxygen atoms may be included without any other heteroatoms.
R 5 -R 6 Independently selected from any one of no, substituted or unsubstituted chains or rings, chain or ring-based formed polymeric units; at R 5 And/or R 6 In the case of representing polymerized units, it comprises- [ M ] 1 -M 2 ]-polymerized units or with- [ M 1 -M 2 ]-different other polymerized units; if the polymer material structure is unfolded, then a single- [ M ] 1 -M 2 ]-the polymerized units are arranged in blocks, in alternating fashion, in periodic fashion, in gradient fashion or in random fashion with respect to the single other polymerized unit.
R 5 And/or R 6 Selected from chains or rings containing or not containing substituents, which represent the end groups of the polymeric material, which are formed on the basis of residues after the reaction of the starting materials or the initiator.
m is selected from 0.01-1, such as 0.02, 0.05, 0.1, 0.2, 0.3, 0.5, 0.8, 1, which means every 1/M- [ M [ ] 1 -M 2 ]-one in the polymerization unit
And M 1 Or M 2 Are connected with each other. When m is 1, the unwritten can be omitted.
p is selected from integers between 10 and 10000, such as 10, 20, 50, 80, 100, 500, 1000, 2000, 3000, 5000, 6000, 8000, 10000, which represent the total of p- [ M ] in the structure of formula 1 1 -M 2 ]-a polymerization unit.
The inventive incorporation of the polymer material of the present application comprises
The polymerization unit of structure, it can promote the security performance of battery, improves battery ion transport, improves battery cycling stability, extension battery life.
In particular, if R 1 -R 6 Independently selected from the group consisting of chains of 1 to 15 atoms, preferably 1 to 10 atoms, more preferably 2 to 6 atoms, including saturated carbon chains, unsaturated carbon chains, saturated heterochains, unsaturated heterochains; the atoms in the chain are selected from C, S, N, O, P, B or Si.
If R is 1 -R 6 Independently, a ring is a three-to eighteen-membered ring, preferably a four-to ten-membered ring, more preferably a five-to eight-membered ring, such as a five-membered ring, a six-membered ring, etc. The ring comprises a monocyclic ring, a bicyclic ring, a bridged ring or a spiro ring, the atoms on the ring are selected from C, P, S, si, N or O, and the monocyclic ring comprises a saturated carbocyclic ring, an unsaturated carbocyclic ring, a saturated heterocyclic ring, an unsaturated heterocyclic ring (-C = O), an aromatic carbocyclic ring and an aromatic heterocyclic ring.
The substituent group comprises: H. halogen atom, = O, = S, alkyl, heteroalkyl, alkenyl, heteroalkenyl, alkynyl, heteroalkynyl, hydroxyl, carbonyl, aldehyde group, carbonate group, haloformyl group, carboxyl group, ester group, peroxy group, amine group (primary amine, secondary amine, tertiary amine, quaternary ammonium salt), imino group (C = N), imide (C (= O) NC (= O)), azo group, nitrate ester (RONO)), and the like 2 ) Phosphate group, thioether group, disulfide group, cyano group, sulfonic group, sulfonyl group, amide group, nitro group, pyridyl group, acyloxy group, phenyl group, benzyl group, benzyloxy group, phenoxy group, acetyl group, benzoyl group, benzyloxycarbonyl group, and a chain or combination thereofThe ring, any one of the above substituents H may be substituted by halogen, preferably by F.
Alternatively, R 3 -R 4 Independently selected from any one of saturated carbon chain or unsaturated carbon chain consisting of no carbon atoms and 1-10 carbon atoms.
Wherein, the P atom has at least one bond to be connected with the C atom on the chain, and compared with the direct connection of all bonds of all P atoms with hetero atoms or with rings, the P atom can promote the exertion of the action of phosphorus groups and is more favorable for improving the safety of polymer materials.
Alternatively, R 1 Comprises at least one unsaturated bond including double bonds, triple bonds and/or comprises at least one heteroatom comprising N, O, P, S, si, F;
preferably, the unsaturated bond is = O;
more preferably, R 1 In at least one
R 1 Can also comprise a plurality of->
wherein-O is either P or M 1 Directly linked or indirectly linked through chains and/or loops, -C = O and P or M 1 Directly or indirectly via chains and/or loops. For the definition of chains and loops herein, reference is made to the above description and no further description is made.
The ester group is contained between the P and the double bond, so that the electrochemical properties of the battery, such as first effect, capacity retention rate and the like, can be effectively improved, the safety of the battery can be improved, and the service life of the battery can be prolonged.
Alternatively, R 1 Is selected from
-O or-C = O is directly linked to P;
preferably, -C = O and M 1 Are connected indirectly through a chain consisting of 1 to 10 atoms;
more preferably, -C = O and M 1 Are connected indirectly through a chain of 2-8 atoms. The arrangement is beneficial to improving the mechanical property of the material.
The polymeric material of claim 1, wherein R is 3 Is selected from
OR-OR, R is selected from any one of H, li, halogen atom, chain OR ring containing substituent OR not;
preferably, the OR is OLi;
preferably, the substituted or unsubstituted chain or ring is a chain or ring consisting of 1 to 8 atoms;
alternatively, R 3 Is selected from
OR-OR, R is selected from any one of H, li, halogen atom, chain OR ring containing substituent OR not containing substituent;
preferably, the OR is OLi;
preferably, the substituted or unsubstituted chain or ring is a chain or ring consisting of 1 to 8 atoms;
R 3 preferably, it is
The ring structure in the substituent directly bonded to the P atom can improve the ability to suppress the temperature rise of the battery, thereby providing higher safety to the battery.
Preferably, A 1 The substituents represented are substituted by one or more halogen atoms, preferably F.
Preferably, the halogen atom is F and the chain comprises at least one heteroatom.
Optionally, the
The cyclic structure represented is selected from monocyclic or polycyclic, saidThe monocyclic ring is selected from a saturated carbocycle, a saturated heterocycle, an unsaturated carbocycle or an unsaturated heterocycle which are three-twelve-membered, and the polycyclic ring is selected from a parallel ring, a bridge ring, a spiro ring and a linked ring which are formed by combining any two monocyclic rings based on the monocyclic ring;
preferably, the monocyclic ring is selected from a five-to six-membered unsaturated carbocyclic or heterocyclic ring;
more preferably, the monocyclic ring is selected from five-six membered unsaturated heterocycles.
Alternatively, R 5 Or R 6 Is selected from [ M ] 3 -M 4 ]-polymerized units of said- [ M [ ] 3 -M 4 ]-the structure of the polymerized units is represented by formula 2:
the structure of the polymeric material is selected from:
wherein M is 3 Selected from C, N, P, S, si, M 4 Selected from C, O, N, P, S, si;
R 10 -R 14 independently selected from any one of no, substituent-containing or substituent-free chains or rings;
n is selected from integers 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 to 800, indicating the total presence of n- [ M ] s in the structure 3 -M 4 ]-a polymerization unit.
In the case of a spread of polymeric material structures, a single- [ M ] 1 -M 2 ]Polymerized units with a single- [ M ] 3 -M 4 ]-the polymerized units are arranged in blocks, in alternating fashion, in periodic fashion, in gradient fashion or in random fashion.
Alternatively, the structure- [ M ] is represented by H1 1 -M 2 ]One monomer unit of the polymerized unit
Is represented by H2 to form- [ M ] 3 -M 4 ]-one monomer unit of the polymerization unit->
M in H1, H2 monomer units 1 、M 3 Left side and M 2 、M 4 The "-" drawn on the right side means that it is linked to other H1 or H2 monomer units via this bond, rather than-CH 3 Abbreviations of (a).
In the polymer material, the arrangement between H1 and H2 includes:
arranged in blocks:
in this case, the first one->
Denotes one or more repeatedly arranged H1, the second->
H2 representing one or more repeating arrangements;
arranged in an alternating manner: one or more H1 s alternate with one or more H2 s in sequence, e.g.
(one H1, one H2 are arranged alternately),. Or>
(two H1, one H2 are arranged alternately),. Or>
(three H1, one H2 are alternately arranged), etc., and the description thereof is omitted. In this case, it is preferable that the light-emitting element,/>
the term "represents one or more of the repetition.
Arranged in a periodic manner: forming a plurality of periods through one or more H1 and one or more H2 respectively, wherein the plurality of periods are arranged in sequence; such as
Etc., a bracket represents a period, and>
representing one or more repeating cycles.
Arranged in a gradient fashion: the composition of H1 and H2 gradually changes along the chain; such as
Indicates H1, H2 increasing with chain gradient.
Random arrangement: one or more H1 s are arbitrarily crossed with one or more H2 s. Such as
/>
Etc., and will not be described herein. In this case, is present>
Represents the random repetition of H1 and H2.
Alternatively, R 14 Selected from rings or chains containing at least one heteroatom, any position of which can be substituted by a substituent;
preferably, R 14 Selected from a ring or chain containing at least two heteroatoms and comprising at least one = O in the ring or chain;
more preferably, R 14 Selected from the group consisting of:
wherein A is 1 、A 2 Meaning that the atoms in the ring/chain can be substituted by substituents.
It should be noted that, in the technical solutions provided in the present application, no matter what synthesis method or process is adopted, the polymer material shown in formula 1 can be formed through the reaction of the raw material a itself or the reaction between the raw material a and the raw material B, and if in some special cases, the raw material a itself or the raw material a and the raw material B also obtain other products, these products are also within the protection scope of the present application.
Optionally, the polymeric material has a structure wherein m is selected from 0.1 to 1, p is selected from integers between 30 and 8000, n is selected from integers between 10 and 800, and p > n.
Optionally, the polymer material is prepared based on at least the reaction of raw material A, or based on at least the reaction of raw material A and raw material B;
the structure of the raw material A is
The structure of raw material B is->
The present application also provides an electrolyte comprising a polymeric material as described above, or comprising a starting material for the preparation of said polymeric material as described above.
The application also provides a battery, which comprises any one or more of the following components: a polymeric material as described above, a starting material for preparing said polymeric material as described above, an electrolyte as described above.
Alternatively, the battery may be a liquid battery, a hybrid solid-liquid battery, or an all-solid battery, where the hybrid solid-liquid battery and the all-solid battery are collectively referred to as a solid-state battery.
The application also provides a use of the polymer material in a battery, wherein the polymer material is placed in a battery component or a battery cell of the battery, and the battery is prepared through an ex-situ curing process;
or raw materials for preparing the polymer material are placed in a battery component or a battery core of the battery, and the battery is prepared through an in-situ curing process;
wherein the battery assembly includes electrodes, a separator, and an electrolyte membrane.
Optionally, the ex situ curing of the polymer material into the cell comprises:
(1) Disposing the polymeric material in a cell of the battery, comprising:
adding the polymer material into electrolyte for dissolving, and then injecting into the prepared battery core;
(2) Disposing the polymeric material in a cell component of the battery, comprising:
dissolving the polymer material in a solvent, and coating the polymer material on an electrode plate, a diaphragm or independently forming a film to form the electrode plate, the diaphragm or an electrolyte film with the polymer material coating; or blending the polymer material in the positive and negative electrode slurry to form the pole piece containing the polymer material.
Optionally, the solvent comprises one or more of ethylene carbonate, fluoroethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, butylene 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, dimethyl sulfoxide;
and then in the process of dissolving the polymer material in a solvent, adding an auxiliary agent, wherein the auxiliary agent comprises any one or more of the following components: lithium salt, inorganic oxide particles, fast ion conductors.
The lithium salt is selected from lithium trifluoromethanesulfonate (LiCF) 3 SO 2 ) Lithium bis (trifluoromethylsulfonic acid) imide (LiN (CF) 3 SO 2 ) 2 ) Lithium hexafluorophosphate (LiPF) 6 ) Lithium tetrafluoroborate (LiBF) 4 ) Lithium perchlorate (LiClO) 4 ) Lithium bis (oxalato) borate (LiBOB), lithium bis (oxalato) borate (LiDFOB), lithium chloride (LiCl), lithium iodide (LiI), lithium bis (fluorosulfonyl) imide (LiFSI), lithium hexafluoroarsenate (LiAs F) 6 ) One or more of (a).
The inert inorganic particles are selected from SiO 2 、ZrO 2 、Al 2 O 3 、TiO 2 、BaTiO 3 、CeO 2 、CuO、ZnO、MnO、MnO 2 Silicates, aluminosilicates, borosilicates and compounds of formula A x B y O z Or any of the above 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, x, y, z are the number of the respective atoms such that the total charge of the salt of an oxyacid is 0.
The active fast ion conductor is an oxide solid electrolyte, and the oxide solid electrolyte particles comprise any one or a combination of at least two of the following compounds: li1+ x of NASICON structure 1 Alx 1 Ge 2 -x 1 (PO 4 ) 3 Or isomorphous heteroatom doped compound thereof, li1+ x 2 Alx 2 Ti 2 -x 2 (PO 4 ) 3 Or isomorphous heteroatom doped compound thereof, and Li with perovskite structure 3 x 3 La 2/3 -x 3 TiO 3 Or isoatomic doped compound of the same crystal type, li 3/8 Sr 7/16 Ta 3/4 Hf 1/4 O 3 Or isomorphous heteroatom doped compound thereof, li 2 x 4 -y 1 Sr 1 -x 4 Tay 1 Zr 1 -y 1 O 3 Or isomorphic heteroatomic doping compound thereof and Li with anti-perovskite structure 3-2 x 5 Mx 5 Ha l O、Li 3 OCl or isomorphous heteroatom doped compound thereof, 2Li4-x6Si1-x6Px6O4 with LISICON structure or isomorphous heteroatom doped compound thereof, and Li 14 ZnGe 4 O 16 Or isomorphous heteroatom doped compound thereof, and Li of garnet structure 7 -x 7 La 3 Zr 2 -x 7 O 12 Or isomorphic heteroatom doped compound thereof, wherein, 0<x 1 ≤<Form x of crystal 0<x 2 ≤<x crystal, type 0.06 hetero 3 Less than or equal to type 06, type 0.25 different 1 ≤.，x 4 ＝0.75y 1 ，00. 5 ≤0.75，0.575 6 ≤.57；0.5 7 <1; wherein M comprises Mg 2+ 、Ca 2+ 、Sr 2+ Or Ba 2+ Hal is an element Cl or I.
Optionally, the in-situ curing of the feedstock into the cell comprises:
(1) Placing the feedstock in a cell of the battery, comprising:
adding the raw materials and an initiator into electrolyte, and forming a solid-state battery with an integrated battery core through in-situ solidification; or at least one raw material is preset in the battery assembly, an initiator and the rest raw materials are added into electrolyte, and then injected into the prepared battery cell, and the battery cell integrated solid-state battery is formed through in-situ solidification;
(2) Placing the feedstock in a cell component of the cell, comprising:
the raw materials are prepared into precursor liquid which is coated on an electrode plate, a diaphragm or a single film, and the precursor liquid is cured in situ to form the electrode plate, the diaphragm or the electrolyte film with the polymer material coating.
Alternatively, in the case that the raw material includes the raw material a and the raw material B, the molar ratio of the raw material B to the raw material a may be 0 to 1, for example, 0, 0.1, 0.2, 0.5, 0.8, 0.9, 1, etc., and the total mass of the raw material a and the raw material B accounts for 1% to 50% of the total mass of the precursor liquid. Preferably 1% to 10%, more preferably 1% to 5%, such as 1%, 2%, 3%, 4%, 5% and the like. And uniformly mixing the lithium salt, the additive, the organic solvent, the raw material A, the raw material B and the initiator at the humidity with the dew point lower than-45 ℃ to obtain the precursor solution.
The mass fraction of the lithium salt in the precursor solution is 5% to 30%, preferably 10% to 25%, more preferably 15% to 20%.
The organic solvent is one or more of ethylene carbonate, fluoroethylene carbonate, vinylene carbonate, ethylene carbonate, propylene carbonate, butylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl 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, delta-valerolactone, tetrahydrofuran, 2-methyltetrahydrofuran, 1, 3-dioxolane, 4-methyl-1, 3-dioxolane, 2-methyl-1, 3-dioxolane, ethylene glycol dimethyl ether, polyethylene glycol, sulfolane, triglyme, fluorinated 1, 4-dimethoxybutane, bis (2, 2-trifluoroethyl) ether, tetramethylsilane, and tetraglyme.
The mass fraction of the organic solvent in the precursor solution is 1% to 90%, preferably 10% to 80%, more preferably 20% to 60%, such as 30%, 40%, 50%, etc.
The initiator is one or more of Azodiisobutyronitrile (AIBN), azodiisoheptanonitrile (ABVN), azodiisobutyronitrile dimethyl ester (AIBME), dibenzoyl peroxide (BPO), tert-Butyl Peroxybenzoate (BPB), methyl ethyl ketone peroxide or a composite initiator system (such as AIBN-ABVN or BPO-BPB).
The mass fraction of the initiator in the precursor solution is 0.001% to 0.5%, preferably 0.005% to 0.3%, more preferably 0.01% to 0.2%, such as 0.015%, 0.05%, 0.1%, 0.15%, etc.
The additive comprises one or more of fluoroethylene carbonate, vinylene carbonate, trimethyl phosphate, triethyl phosphate, succinic anhydride, 18-crown-6, triphenyl phosphite, ethylene carbonate, trimethyl borate, lithium difluorobis (oxalate), lithium tetrafluoro (oxalate), tributyl phosphate, biphenyl, vinyl sulfite, difluorodiphenylsilane, lithium difluorosulfimide, tributyl borate, ethoxy pentafluorocyclotriphosphazene, vinyl sulfate, lithium nitrate, 1, 3-propane sultone, lithium difluorophosphate, diethyl sulfite and succinonitrile.
The battery cell comprises a positive electrode, a negative electrode and a diaphragm arranged between the positive electrode and the negative electrode.
Optionally, the positive active material may include one or more of lithium iron phosphate, lithium iron manganese phosphate, lithium cobaltate, lithium manganate, lithium nickel cobalt aluminate, lithium rich manganese; the negative active material may include one or more of graphite, silicon, soft carbon, hard carbon, a silicon-carbon composite material, silicon oxycarbon, lithium titanate, mesocarbon microbeads, molybdenum disulfide, silicon oxide, silicon, metallic lithium, or a metallic lithium alloy; the diaphragm can be one of a polyolefin diaphragm, a cellulose diaphragm, a polyimide diaphragm, a polyamide diaphragm, an aramid diaphragm, a PET non-woven fabric diaphragm, a ceramic coating diaphragm, a solid electrolyte coating diaphragm and a PVDF coating diaphragm.
In practical applications, the electrolyte may be a commercial electrolyte currently used in lithium secondary batteries, or may be configured autonomously, and the composition and ratio thereof are not particularly limited in the present invention.
The technical effects are as follows:
the polymer material containing the phosphorus group is innovatively provided, and can be flexibly applied to a battery, so that the safety of the battery is improved, the ion transmission of the battery is improved, the cycling stability of the battery is improved, and the service life of the battery is prolonged.
The polymer material provided by the application comprises a special structure shown as a formula 1, and the safety and the cycling stability of the battery are greatly improved through a solid-state battery prepared by an ex-situ curing or in-situ curing method.
In addition, the in-situ curing method can greatly improve the interface contact condition of substances (such as electrolyte) in the battery and the pole piece, and reduce polarization and interface impedance, thereby improving the electrical properties of the battery, such as energy density exertion, cycle frequency and the like, greatly improving the electrochemical property of the battery, and prolonging the service life of the battery. And the in-situ curing preparation process is simple, safe and environment-friendly, greatly reduces the use and discharge of organic solvents, is compatible with the existing liquid battery process, and is easy to rapidly promote industrialization. Compared with a non-in-situ curing process, the in-situ curing process can better improve the safety and the electrochemical performance of the battery.
Drawings
FIG. 1 is a graph comparing the cycle curves of the batteries of test example 1 of the present application;
fig. 2 is a graph comparing the results of the battery puncture test in test example 2 of the present application.
Detailed Description
The following description of specific embodiments of the present application refers to the accompanying drawings.
In the present invention, unless otherwise specified, scientific and technical terms used herein have the meanings that are commonly understood by those skilled in the art. Also, the reagents, materials and procedures used herein are those that are widely used in the corresponding fields. Meanwhile, in order to better understand the present invention, the following provides definitions and explanations of related terms.
In the examples of the present application, the polymerization degrees p and n of the polymeric units in the polymer material structure can be calculated by a number average molecular weight method.
The Number-average Molecular Weight (Number-average Molecular Weight) is the most commonly used method for calculating the degree of polymerization. The polymer material is composed of polymerization units with the same chemical composition and different polymerization degrees, and the number average molecular weight (Mn) can be obtained by statistical averaging according to the number of molecules. Number average molecular weight = sum of molecular weight of each component moles per total moles. The formula for calculating the number average molecular weight is the prior art, and is not described in detail herein.
Nuclear magnetic hydrogen spectrum in the present example 1 In H 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 a quintet, a sextet, etc.), and dd representsDouble doublet, dt represents double triplet; the numbers in the front of the brackets indicate the chemical shift, and the numbers in the brackets in front of H indicate the number of H, such as 2.22 (s, 2H), i.e. the chemical shift is 2.22 for two H, and the peak shows a single peak. Other situations can be analogized and are not described in detail.
In this example, MS (ESI) M/z is (M-H) + Represents a mass spectrum.
In the examples of the present application, the english abbreviations correspond to the following: ethyl Methyl Carbonate (EMC), diethyl carbonate (DEC), ethylene Carbonate (EC); lithium nitrate (LiNO) 3 ) Fluoroethylene carbonate (FEC), vinyl sulfate (DTD), lithium tetrafluoro oxalate phosphate (LiPC) 2 O 2 F 4 ) 1, 3-propane sultone (1, 3-PS), lithium difluorophosphate (LiPO) 2 F 2 ) Vinylene Carbonate (VC); lithium difluoroborate (LiODFB) and lithium hexafluorophosphate (LiPF) 6 ) Lithium bis (fluoromethylsulfonyl) imide (LiFSI); azobisisobutyronitrile (AIBN), dibenzoyl peroxide (BPO).
In the examples of the present application, 0.5C/0.5C means charging at 0.5C rate and discharging at 0.5C rate.
In the present application, a polymer material may be placed in a battery component or cell of the battery, and the battery is prepared by an ex-situ curing process;
or raw materials for preparing the polymer material are placed in a battery component or a battery core of the battery, and the battery is prepared through an in-situ curing process. Wherein the battery assembly includes an electrode, a separator, and an electrolyte membrane.
The ex situ curing means for placing the polymeric material in the cell comprises:
(1) Placing the polymeric material in a cell of the battery; the method specifically comprises the following steps: adding the polymer material into electrolyte for dissolving, and then injecting into the prepared battery core;
(2) Placing the polymeric material in a cell component of the cell; the method specifically comprises the following steps:
dissolving the polymer material in a solvent, and coating the polymer material on an electrode plate, a diaphragm or independently forming a film to form the electrode plate, the diaphragm or an electrolyte film with the polymer material coating; or the polymer material is blended in the positive and negative electrode slurry to form a pole piece containing the polymer material;
the in situ curing mode of placing the raw material in the battery comprises the following steps:
(1) Placing the feedstock in a cell of the battery; the method specifically comprises the following steps: adding the raw materials and an initiator into an electrolyte, and forming a solid-state battery with an integrated battery core through in-situ solidification; or at least one raw material is preset in the battery assembly, the initiator and the rest raw materials are added into the electrolyte, and then the electrolyte is injected into the prepared battery cell, and the solid-state battery with the integrated battery cell is formed by in-situ solidification.
(2) Placing the feedstock in a cell component of the cell; the method specifically comprises the following steps:
the raw materials are prepared into precursor liquid to be coated on an electrode plate, a diaphragm or a single film, and the precursor liquid is cured in situ to form the electrode plate, the diaphragm or an electrolyte film with a polymer material coating.
It should be noted that the application modes presented in the following examples are only preferred application modes for the raw material/battery material, and other application modes of in-situ curing or non-in-situ curing can also be applied.
Example 1
Raw material A1:
raw material B1: />
The preparation method comprises the following steps: raw material A1: by passing
(CAS: 79-41-4) and->
(CAS: 1707-03-5) esterification reaction is carried out under acid catalysis to obtain the raw material A1.
Raw material B1: under the protection of nitrogen, 0.2mmol of the compound was added into a 25mL Schlenk tube
2mL of dry dichloromethane is cooled to 0 degree of dryness, 0.2mmol of acryloyl chloride is dropwise added, the mixture is stirred and reacted for 1 hour after the addition is finished, the mixture is returned to room temperature for reaction for 1 hour, 5mL of water is added, 3 is used for extraction with the dichloromethane at the room temperature, organic phases are combined, saturated NaCl is washed, anhydrous sodium sulfate is dried, suction filtration is carried out, reduced pressure distillation is carried out, and column chromatography is carried out to obtain ion column>
Under the protection of nitrogen, 0.2mmol of the compound was added into a 25mL Schlenk tube
2mL of dried tetrahydrofuran is cooled to-78 IV, n-butyllithium n-hexane solution is dripped, stirring is carried out for 30min after the addition is finished, stirring is carried out for 1h after the temperature is returned to room temperature, and reduced pressure distillation is carried out to obtain a raw material B1.
Nuclear magnetic resonance hydrogen 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)。
Nuclear magnetic resonance hydrogen 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)。
The application mode is as follows: adding the raw materials A1 and B1 and an initiator into the electrolyte to prepare a precursor solution, and injecting the precursor solution into the battery cell for in-situ curing.
The raw material A1 and the raw material B1 are copolymerized to form a copolymer containing 200H A1 Polymeric units and 80H B1 Polymeric material consisting of polymerized units, the structure of which is mainly according to five H A1 Polymerized units of one H B1 The polymerized units are arranged in an alternating manner.
Wherein H A1 The structure of the polymerized unit is
-Q1 is-CH 3 -Q2 is->
m is 1, p is 200.
H B1 The structure of the polymerized unit is
-Q3 is absent, -Q4 is->
n is 80.
Example 2
Raw material A2:
raw material B2: />
The preparation method comprises the following steps: the raw material A2 is the existing substance, and the CAS is 60421-10-5;
starting material B2 preparation method starting material A1 from example 1 was prepared by
(CAS: 79-10-7) with
(CAS: 1433993-67-9) to obtain a raw material B2;
starting material A2 MS (ESI) M/z 593.15 (M-H) + (ii) a Feedstock B2 MS (ESI) M/z 208.00 (M-H) + 。
The application mode is as follows: and adding the raw materials A2 and B2 and an initiator into the electrolyte to prepare a precursor solution, and injecting the precursor solution into the battery cell for in-situ solidification.
The raw material A2 and the raw material B2 are copolymerized to form a copolymer of 10000H A2 Polymerized units and 1000H B2 Polymeric material consisting of polymerized units, the structure of which is predominantly arranged in blocks.
Wherein H A2 The structure of the polymerized unit is
-Q1 is-CH 3 -Q2 is
m is 1, p is 10000.
H B2 The structure of the polymerized unit is
-Q3 is-CH 3 -Q4 is->
n is 1000.
Example 3
Raw material A3:
raw material B3: />
/>
The preparation method comprises the following steps: starting material A3 is the existing material, reaxyz ID:32890736, MS (ESI) M/z 540.15 (M-H) + 。
Raw material B3: adding 0.2mmol of sulfonate substrate 1 and 2mL of dry dichloromethane into a 25mL Schlenk tube, freezing by liquid nitrogen, replacing with nitrogen in vacuum, returning to room temperature, adding 0.2mmol of NBS under the protection of nitrogen, heating to 40, stirring for reaction for 8 hours, terminating the reaction, carrying out reduced pressure distillation, and carrying out column chromatography to obtain an intermediate substituted by bromine at the final position of the olefin double bond alpha of the sulfonate substrate. The bromine-substituted intermediate of the previous step was added to 2mL of dichloromethane, benzyltriethylammonium chloride (TEBAC), 0.2mmol of NaF,40F were added, and the reaction was stirred for 8h. Cooling to room temperature, adding 5mL of water, extracting with 3. About.t. dichloromethane, combining the organic phases, washing with saturated NaCl, drying over anhydrous sodium sulfate, filtering, vacuum distilling, and column chromatography to obtain fluorinated sulfonate intermediate
Adding 0.2mmol of intermediate 2 into a 25mL Schlenk tube under the protection of nitrogen, dropwise adding 200mmol of sodium dry borane tetrahydrofuran complex, stirring at room temperature for 30min, sequentially adding 70 parts of sodium hydroxide, then adding 20 parts of hydrogen peroxide oxide (30 percent by weight), stirring for 30min, adding 5mL of dichloromethane, 5mL of water, 3, L of alkane and dichloromethane, extracting, combining organic phases, washing with saturated NaCl, drying with anhydrous sodium sulfate, filtering, distilling under reduced pressure, and carrying out column chromatography to obtain the intermediate
Under the protection of nitrogen, 0.2mmol of intermediate is added into a 25mL Schlenk tube
Adding 0.2mmol of acryloyl chloride dropwise into 2mL of dried dichloromethane, stirring at room temperature for 30min, stopping reaction, adding 5mL of water, extracting with 3, using reaction dichloromethane, combining organic phases, washing with saturated NaCl, drying with anhydrous sodium sulfate, performing suction filtration, performing reduced pressure distillation, and performing column chromatography to obtain a raw material B3.MS (ESI) M/z 224.02 (M-H) + 。
The application mode is as follows: and adding the raw materials A3 and B3 and an initiator into the electrolyte to prepare a precursor solution, and injecting the precursor solution into the battery cell for in-situ solidification.
The raw material A3 and the raw material B3 are copolymerized to form a copolymer consisting of 250H A3 Polymerized units and 5H B3 Polymeric material consisting of polymerized units, the structure of the polymeric material being predominantly randomly arranged.
Wherein H A3 The structure of the polymerized unit is
-Q1 is-CH 3 -Q2 is
m is 1 and p is 250.
H B3 The structure of the polymerized unit is
-Q3 is-CH 3 -Q4 is->
n is 5.
Example 4
Raw material A4:
raw material B4: />
/>
The preparation method comprises the following steps:
raw material A4: under the protection of nitrogen, 0.2mmol of the compound was added into a 25mL Schlenk tube
2mL of dried tetrahydrofuran is cooled to-78 IV, 0.2mmol of n-butyllithium n-hexane solution is dripped in, after the addition is finished, the mixture is stirred for half an hour, the mixture returns to the room temperature, and the raw material A4 is obtained by reduced pressure distillation.
Raw material B4: under nitrogen protection, 0.2mmol of substrate was added to a 25mL Schlenk tube
Sequentially dropwise adding 0.2mmol of liquid bromine and 3.6 mu L of water into 2mL of 1, 4-dioxane, heating to 90 ℃ after the addition, reacting for 6h, adding 5mL of water, extracting with 3X 5mL of dichloromethane, combining organic phases, washing with saturated NaCl, drying with anhydrous sodium sulfate, performing suction filtration, performing reduced pressure distillation, and performing column chromatography to obtain an intermediate (ion exchange membrane ion exchanger)>
Adding 0.2mmol of intermediate 4 into 25mL Schlenk tube under nitrogen protection, adding 2mL dry dichloromethane, cooling to 0 deg.C, adding 0.2mmol DAST reagent (diethylaminosulfur trifluoride), reacting for 1h, distilling under reduced pressure, and performing column chromatography to obtain intermediate
Will->
And NaOH are added to an acetonitrile solvent containing 20% water and heated at 80 ℃ for 8h to obtain the intermediate->
Under nitrogen protection, 0.2mmol of intermediate was added to a 25mL Schlenk tube
Adding 1mL of dry dichloromethane, cooling to 0 ℃, dropwise adding a newly prepared butenoyl chloride dichloromethane mixed solution, reacting for 1h after the addition is finished, reacting for 1h at room temperature, adding 5mL of water, extracting with 3X 5mL of dichloromethane, combining organic phases, washing with saturated NaCl, drying with anhydrous sodium sulfate, performing suction filtration, performing reduced pressure distillation, and performing column chromatography to obtain a raw material B4.
Nuclear magnetic resonance hydrogen 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)。
Nuclear magnetic resonance hydrogen 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)。
The application mode is as follows: and adding the raw materials A4 and B4 and an initiator into the electrolyte to prepare a precursor solution, and injecting the precursor solution into the battery cell for in-situ solidification.
The raw material A4 and the raw material B4 are copolymerized to form a copolymer with 40H A4 Polymerized units and 10H B4 Polymeric material of polymerized units, H in the structure of the polymeric material A4 、H B4 Mainly according to a periodic arrangement of 10H A4 And 1H B4 Is one period (H) A4 -H A4 -H A4 -H A4 -H A4 -H A4 -H A4 -H A4 -H A4 -H A4 -H B4 )。
Wherein H A4 The structure of the polymerized unit is
-Q1 is-CH 3 -Q2 is->
m is 1 and p is 40./>
H B4 The structure of the polymerized unit is
-Q3 is absent, -Q4 is->
n is 10.
Example 5
Raw material A5:
raw material B5: />
The raw material A5 is the existing material, CAS:869483-26-1, MS (ESI) M/z 284.10 (M-H) + 。
Raw material B5 is a conventional material, CAS:18133-42-1, MS (ESI) M/z 111.99 (M-H) + 。
The application mode is as follows: and (3) presetting the raw material A5 at the anode, adding an initiator and the raw material B5 into the electrolyte, and injecting the electrolyte into the prepared battery cell for in-situ solidification.
The raw material A5 and the raw material B5 are copolymerized to form a copolymer containing 30H A5 Polymerized units and 30H B5 Polymeric material of polymerized units, H in the structure of the polymeric material A5 、H B5 Mainly in a random arrangement.
Wherein H A5 The structure of the polymerized unit is
-Q1 is none, -Q2 is->
m is 1 and p is 30.
H B5 The structure of the polymerized unit is
-Q3 is none, -Q4 is->
n is 30.
Example 6
Raw material A6:
raw material B6: />
The preparation method comprises the following steps: the starting material A6 is the existing material, CAS is 191105-63-2, MS (ESI) M/z 368.14 (M-H) + 。
Raw material B6: by passing
Prepared by fluoro to give an intermediate>
Under the protection of nitrogen, 0.2mmol of the intermediate is added to a Sc hlenk tube of 25mL>
2mL of dried dichloromethane and 0.2mmol of NBS, heating to 40 percent after the addition, stirring for 8 hours, stopping the reaction, distilling under reduced pressure, and performing column chromatography to obtain an intermediate which is/the vessel>
0.2mmol of intermediate was added to a 25mL reaction tube
100 mu L (3M) NaOH, stirring at room temperature after the additionStirring for 8h, terminating the reaction, adding 5mL of dichloromethane and 5mL of water, extracting with 3X 5mL of dichloromethane, combining organic phases, washing the organic phase with saturated NaCl, drying with anhydrous sodium sulfate, performing suction filtration, performing reduced pressure distillation, and performing column chromatography to obtain an intermediate (ion-collecting/ion-collecting) ion-exchange membrane>
Under nitrogen protection, 0.2mmol of intermediate was added to a 25mL Schlenk tube
2mL of dichloromethane, cooling to 0 ℃, dropwise adding 0.2mmol of acryloyl chloride, reacting for 1h after the addition, returning to room temperature for 1h, adding 5mL of water, extracting with 3X 5mL of dichloromethane, mixing organic phases, washing the organic phase with saturated NaCl, drying with anhydrous sodium sulfate, vacuum filtering, distilling under reduced pressure, and performing column chromatography to obtain intermediate>
Under the protection of nitrogen, 0.2mmol of intermediate 5 and 2mL of dried tetrahydrofuran are added into a 25mL Schlenk tube, the mixture is cooled to-78 ℃,0.2mmol of n-butyllithium (n-hexane solution) is added dropwise, the reaction is carried out for 30min after the addition is finished, the mixture returns to the room temperature, and reduced pressure distillation is carried out, so that the raw material B6 is obtained. MS (ESI) M/z 188.02 (M-H) + 。
The application mode is as follows: and (3) presetting the raw material A6 in a diaphragm, adding an initiator and the raw material B5 into the electrolyte, and injecting the electrolyte into the prepared battery cell for in-situ solidification.
The raw material A6 and the raw material B6 are copolymerized to form 4000H A6 Polymerized units and 800H B6 Polymeric material of polymerized units, H in the structure of the polymeric material A6 、H B6 Mainly in a random arrangement.
Wherein H A6 The structure of the polymerized unit is
-Q1 is-CH 3 -Q2 is->
m is 1 and p is 4000.
H B6 The structure of the polymerized unit is
-Q3 is-CH 3 -Q4 is->
n is 800.
Example 7
Raw material A7:
raw material B7: />
The preparation method comprises the following steps: the raw material A7 is the existing material CAS:2429914-94-1, and the nuclear magnetic resonance hydrogen spectrum of the raw material A7 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)。
Raw material B7: firstly, the method
And &>
Amidation reaction takes place to obtain->
(see Nature Communications,12 (1), 930, 2021.DOI 10.1038/s 41467-021-21190-8), then bromo-harvesting ` at the benzyl position using NBS free radical reaction>
(see Malaria Journal,13,190/1-190/26, 2014.DOIα of the acylic sulfide, then hydrogen is abstracted, and nucleophilic substitution with the substrate of benzyl bromide occurs to obtain the starting material B7 (see Chemical communications, 47 (41), 11465-11467, 2011. Doi. Nuclear magnetic resonance hydrogen spectrum of raw material B7 1 HNMR(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)。
The application mode is as follows: the raw materials A7 and B7 are preset in the positive electrode slurry, the mixture is coated on an aluminum foil after being uniformly mixed, an initiator solution is added into an electrolyte, then the electrolyte is injected into a prepared battery cell, and in-situ solidification is carried out for 6 hours at 50 ℃ to form a positive electrode plate with a battery material.
The raw material A7 and the raw material B7 are copolymerized to form 1000 groups of H A7 Polymeric units and 360H B7 Polymeric material of polymerized units, H in the structure of the polymeric material A7 、H B7 Mainly in a random arrangement.
Wherein H A7 The structure of the polymerized unit is
-Q1 is none, -Q2 is->
m is 1, p is 1000.
H B7 The structure of the polymerized unit is
-Q3 is-CH 3 -Q4 is->
n is 360.
Example 8
Raw material A8:
raw material B8: />
The preparation method comprises the following steps: the raw material A8 is the existing material, and the CAS is 2230541-46-3.MS (ESI) M/z 286.08 (M-H) + 。
Raw material B8:
firstly, n-butyl lithium is used for extracting hydrogen from sulfonyl lactone, then nucleophilic addition is carried out on sulfonyl lactone and cyclohexanone, and alcohol is obtained by hydrolysis
In the second step, the raw material B8 is obtained by esterification reaction of the raw material and acrylic acid. (Ref 1: azerbaidzanskii Khimichiskii Zhurna l, (2), 131-134; 2009). MS (ESI) M/z 274.09 (M-H) + 。
The application mode is as follows: and preparing the raw materials A8 and B8 into precursor liquid, coating the precursor liquid on the surface of the anode, and curing in situ to form the anode with the polymer material coating.
The raw material A8 and the raw material B8 are copolymerized to form a copolymer containing 500H A8 Polymerized units and 400H B8 Polymeric material of polymerized units, H in the structure of the polymeric material A8 、H B8 Mainly according to two H A8 Polymerized units of one H B8 The polymerized units are arranged in an alternating manner.
Wherein H A8 The structure of the polymerized unit is
-Q1 is absent, -Q2 is->
m is 1, p is 500.
H B8 The structure of the polymerized unit is
-Q3 is none, -Q4 is->
n is 400.
Example 9
Raw material A9:
MS(ESI)m/z 305.06(M-H) +
raw material B9:
MS(ESI)m/z 194.03(M-H) + the raw material B9 is the existing material, CA S63411-25-6
The preparation method of the raw material A9 comprises the following steps:
the intermediate is obtained by the esterification and hydrolysis of glutaric anhydride and vinyl alcohol
Then, the pyridine phosphoric acid is prepared into lithium alkoxide, and the lithium alkoxide and the intermediate with the equivalent weight prepared before are subjected to esterification reaction to form a raw material A9. (Ref: zhurnal Obshchei Khimii,65 (11), 1924-5.
The application mode is as follows: and preparing the raw materials A9 and B9 into precursor liquid, coating the precursor liquid on the surface of the negative electrode, and curing in situ to form the negative electrode with the polymer material coating.
The raw material A9 and the raw material B9 are copolymerized to form 8000H A9 Aggregate units and 640H B9 Polymeric material of polymerized units, H in the structure of the polymeric material A9 、H B9 Mainly in a random arrangement.
Wherein H A9 The structure of the polymerized unit is
-Q1 is none, -Q2 is->
m is 1, p is 8000.
H B9 The structure of the polymerized unit is
-Q3 is absent, -Q4 is->
n is 640.
Example 10
Raw material A10:
MS(ESI)m/z 334.11(M-H) + (Material A10 is conventional CAS: 2542065-61-0)
Raw material B10:
MS(ESI)m/z 190.11(M-H) + (the raw material B10 is a conventional substance, CAS: 35836-29-4)
The application mode is as follows: and adding the raw materials A10 and B10 and an initiator into the electrolyte to prepare a precursor solution, and injecting the precursor solution into the battery cell for in-situ solidification.
The raw material A10 and the raw material B10 are copolymerized to form a copolymer containing 10H A10 Polymerized units and 9H B10 Polymeric material of polymerized units, H in the structure of the polymeric material A10 、H B10 Mainly in a random arrangement.
Wherein H A10 The structure of the polymerized unit is
-Q1 is->
-Q2 is->
m is 1 and p is 10.
H B10 The structure of the polymerized unit is
-Q3 is absent, -Q4 is->
n is 9.
Example 11
Raw material A11:
MS(ESI)m/z 705.25(M-H) + (A11 is conventional substance, CAS: 68397-51-3)
Raw material B11:
MS(ESI)m/z 187.08(M-H) +
the preparation method of the raw material B11 comprises the following steps:
is hydrolyzed to obtain->
Obtained by oxidation with manganese dioxide (DCM, 80 oxygen)>
Prepared by the coupling reaction of CuCN and bromoalkane
Br 2 Addition was then made with substitution of NaF. Under the protection of nitrogen, 0.2mmol of the compound is added into a 25mL reaction tube
2mL of dried dichloromethane is cooled to 0 dryness, 0.2mmol of liquid bromine is dripped, reaction is carried out at room temperature for 1h after the addition is finished, 1mL of saturated sodium thiosulfate aqueous solution is added until the solution is colorless, 2mL of water is added, extraction is carried out by using 3, thiodichloromethane is used for extraction, organic phases are combined, saturated NaCl is washed, anhydrous sodium sulfate is dried, and reduced pressure distillation is carried out to obtain a crude product. The crude product was added to a 25mL reaction tube and 2mL of dryDried dichloromethane, 0.1mmol benzyltriethylammonium chloride (TEBAC), 0.2mmol NaF, stirring at 40 deg.C for 8 hr, cooling to room temperature, adding water for quenching, extracting with dichloromethane, mixing organic phases, drying, and distilling under reduced pressure to obtain->
The crude product of (1).
Hydrolyzing under alkaline condition. Under the protection of nitrogen, the mixture is prepared
Adding the crude product into a 25mL reaction tube, adding 2mL1, 4-dioxane and 3M NaOH 100 mu L, heating to 90 ℃ for reaction for 8 hours, cooling to room temperature, adding 5mL of water, extracting with 3X 5mL of dichloromethane, combining organic phases, washing the organic phase with saturated NaCl, drying with anhydrous sodium sulfate, performing suction filtration, performing reduced pressure distillation, and performing column chromatography to obtain the product>
Dehydrating and condensing under the condition of acetic anhydride. Under the protection of nitrogen, 0.2mmol of
Adding into 25mL reaction tube, adding 1mL acetic anhydride, heating to 120 deg.C, reacting for 8h, cooling, distilling under reduced pressure, and purifying by column chromatography to obtain the desired blood pressure and blood pressure>
N-butyl lithium is prepared by extracting hydrogen at low temperature and nucleophilic substitution. Under the protection of nitrogen, 0.2mmol of the active carbon
Adding into a 25mL Schlenk reaction tube, adding 2mL of dry tetrahydrofuran, cooling to-78 ℃, dropwise adding n-butyllithium, reacting for 1h after the addition is finished, dropwise adding bromoisoamylene, reacting for 1h at room temperature, adding water for quenching, adding 5mL of water, extracting with 3X 5mL of dichloromethane, combining organic phases, washing the organic phase with saturated NaCl, drying with anhydrous sodium sulfate, filtering, decompressing and decompressingDistilling and carrying out column chromatography to obtain the raw material B11.
The application mode is as follows: preparing the raw materials A11 and B11 into precursor liquid, coating the precursor liquid on the surface of the diaphragm, and curing in situ to form the diaphragm with the polymer material coating.
The raw material A11 and the raw material B11 are copolymerized to form 100H A11 Polymeric units and 75H B11 Polymeric material of polymerized units, H in the structure of the polymeric material A11 、H B11 Predominantly in a block arrangement.
Wherein H A11 The structure of the polymerized unit is
-Q1 is-CH 3 -Q2 is
m is 1 and p is 100./>
H B11 The structure of the polymerized unit is
-Q3 is-CH 3 -Q4 is->
n is 75.
Example 12
Raw material A12:
MS(ESI)m/z 334.11(M-H) + (the raw material A12 is the existing substance, CAS: 936752-22-6)
Raw material B12:
b12 is the existing substance, CAS:1686096-69-4, MS (ESI) M/z 189.98 (M-H) +
The application mode is as follows: and adding the raw materials A12 and B12 and an initiator into the electrolyte to prepare a precursor solution, and injecting the precursor solution into the battery cell for in-situ solidification.
Raw materials A12 and B12 copolymerization to form 600H A12 Polymeric units and 360H B12 Polymeric material of polymerized units, H in the structure of the polymeric material A12 、H B12 Predominantly in block arrangement.
Wherein H A12 The structure of the polymerized unit is
-Q1 is { (R) }>
-Q2 is->
m is 1, p is 600.
H B12 The structure of the polymerized unit is
-Q3 is-O-CH 3 -Q4 is->
n is 360.
Example 13
Battery material G1:
MS(ESI)m/z 3272.54(M-H) +
the application mode is as follows: preparing a polymer material G1, mixing the polymer material G1 into a negative electrode slurry, coating the slurry on a copper foil to obtain a negative electrode containing the polymer material G1, laminating and baking a positive electrode plate, a negative electrode plate and a diaphragm to obtain a dry battery cell, injecting an electrolyte, packaging the battery, and standing at room temperature for 12 hours to fully soak the battery cell to obtain the solid battery containing the polymer material G1.
Example 14
Battery material G2:
MS(ESI)m/z 4132.98(M-H) +
the application mode is as follows: preparing a polymer material G2, adding the polymer material G2 into an electrolyte to dissolve to obtain an electrolyte containing a battery material, laminating and baking a positive pole piece, a negative pole piece and a diaphragm to obtain a dry battery core, injecting the electrolyte into the battery core, packaging the battery, and standing at room temperature for 12 hours to fully soak the battery core to obtain the solid-state battery containing the polymer material G2.
Example 15
Battery material G3:
the application mode is as follows: preparing a polymer material G3, mixing the polymer material G3 into a negative electrode slurry, coating the slurry on a copper foil to obtain a negative electrode containing the polymer material G3, laminating and baking a positive electrode plate, a negative electrode plate and a diaphragm to obtain a dry battery cell, injecting an electrolyte, packaging the battery, and standing at room temperature for 12 hours to fully soak the battery cell to obtain the solid battery containing the polymer material G3.
Example 16
Battery material G4:
the application mode is as follows: preparing a polymer material G4, adding the polymer material G4 into an electrolyte to dissolve to obtain an electrolyte containing a battery material, laminating and baking a positive pole piece, a negative pole piece and a diaphragm to obtain a dry battery core, injecting the electrolyte into the battery core, packaging the battery, and standing at room temperature for 12 hours to fully soak the battery core to obtain the solid-state battery containing the polymer material G4.
Test example 1
1. Preparation of positive pole piece
Uniformly mixing a positive electrode active material, a conductive agent, a binder and a fast ion conductor according to the data proportion listed in tables 1C1-C6 to obtain positive electrode slurry with certain fluidity; then, the positive electrode plate is coated on an aluminum foil, and the surface capacity of the positive electrode plate is controlled to be 4.5mAh/cm 2 Air-blast drying and rolling to obtain the anodeThe tablets are named C1, C2, \8230andC 6, respectively. The conductive agent is carbon nano tube and conductive carbon black (CNT + Super-P, the mass ratio of the CNT + Super-P is 1. The proportion is the mass ratio of the anode main material, the binder, the conductive agent and the fast ion conductor.
The positive electrode material is LiCoO 2 (abbreviated as LCO) and LiNi 0.83 Co 0.12 Mn 0.05 O 2 (abbreviated as Ni 83) and LiNi 0.8 Co 0.15 Al 0.05 O 2 (abbreviated NCA). The fast ion conductor is Li 1.4 Al 0.4 Ti 1.6 (PO 4 ) 3 (abbreviated as LATP), li 6.4 La 3 Zr 1.6 Ta 0.6 O 12 (abbreviated as LLZO).
TABLE 1 Positive Pole piece
2. Preparation of negative pole piece
Adding a main cathode material active substance, a conductive agent and a binder into deionized water according to data listed in Table 2, and uniformly mixing and stirring to obtain cathode slurry with certain fluidity; then, the positive electrode plate is coated on a copper foil, and the surface capacity of the positive electrode plate is controlled to be 4.8mAh/cm 2 The cathode pole piece is obtained by air-blast drying and rolling or the metal lithium is directly used as the cathode and is respectively named as F1, F2, \ 8230and F4. The proportion is the mass ratio of the negative electrode main material, the binder and the conductive agent.
TABLE 2 negative pole piece
| Numbering | Negative electrode | Conductive agent | Binder | Ratio of |
| 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 | —— | —— | —— |
The silicon-carbon material is an SL450A-SOC nano silicon-carbon negative electrode material of Liyang Tianmu lead battery material science and technology Limited, and the silicon-carbon material is an S450-2A silicon-oxygen carbon negative electrode material of Beibei new energy material Limited; the binder is sodium carboxymethylcellulose and styrene butadiene rubber (CMC + SBR).
3. Diaphragm
TABLE 3 membranes
| Numbering | Diaphragm | Specification/grid separator |
| S1 | PP double-sided ceramic | 2+2 (12-substrate 2-alumina ceramic) |
| S2 | PE double-sided ceramic | 2+2 (12-substrate 2-alumina ceramic) |
4. Electrolyte solution
In practical applications, the electrolyte may be a commercial electrolyte currently used in lithium secondary batteries, or may be configured autonomously, and the composition and ratio thereof are not particularly limited in the present invention.
TABLE 4 preparation of the electrolyte
5. Battery assembly
Preparation of batteries 1-4, batteries 10, batteries 12, comparative batteries 1-4, comparative batteries 7-13, comparative batteries 16-18
According to the data listed in Table 5, in an environment with a dew point lower than-45 ℃, the precursor solution is injected into the battery core and stands for 6-12 hours, and is solidified for 6-8 hours at 50-60 ℃ to obtain an in-situ polymerized electrolyte, and then the battery prepared by in-situ solidification is obtained through the working procedures of formation, secondary sealing, capacity grading and the like.
Preparation of Battery 5 and comparative Battery 5
The method comprises the steps of presetting a raw material A5 in a positive pole piece, firstly adding the raw material A5 into slurry of a positive pole C3, uniformly mixing, coating the slurry on an aluminum foil to obtain a positive pole piece containing the raw material A5, laminating and baking the positive pole piece, a negative pole piece and a diaphragm to obtain a dry battery cell, then adding B5 and an initiator into electrolyte, injecting the electrolyte into the prepared battery cell, and carrying out in-situ solidification to obtain the solid battery containing the battery material.
Preparation of Battery 6 and comparative Battery 6
The raw material A6 is preset on a diaphragm, the raw material A6 is prepared into slurry firstly, the slurry is coated on the surface of the diaphragm, and the thickness of the coating is controlled to be 3. Laminating and baking the positive pole piece, the negative pole piece and the diaphragm containing the raw material A6 to obtain a dry battery cell, adding the B6 and an initiator or an independent initiator into an electrolyte, and injecting the electrolyte into the prepared battery cell for in-situ solidification to obtain the solid battery containing the polymer material.
Preparation of Battery 7
According to data listed in table 5, raw materials A7 and B7 (the molar ratio of B7 to A7 is 0.36) are mixed into slurry for preparing a positive electrode C4, the mixture is uniformly mixed and coated on an aluminum foil to obtain a positive electrode of the raw materials A7 and B7, an initiator AIBN is added into an electrolyte E7, the positive electrode sheet, a negative electrode sheet F2 and a diaphragm S2 are laminated and baked to obtain a dry cell, the electrolyte with the initiator is injected, the cell is packaged, and the cell is allowed to stand at room temperature for 12 hours to fully infiltrate the cell, so that a solid-state battery containing a battery material is obtained.
Preparation of Battery 8
According to data listed in Table 5, adding raw materials A8 and B8 (the molar ratio of B8 to A8 is 0.8) and an initiator BPO into a solvent, uniformly mixing to obtain a raw material solution containing a polymer material raw material, coating the raw material solution on the surface of a positive electrode C5, controlling the thickness of the coating to be 2 microns, initiating in-situ polymerization of a monomer at 50 ℃ to obtain a positive electrode plate containing the polymer material coating, laminating and baking the positive electrode plate containing the polymer material coating, a negative electrode plate F1 and a diaphragm S1 to obtain a dry battery cell, injecting an electrolyte E4, packaging the battery, and standing at room temperature for 12 hours to fully infiltrate the battery cell to obtain the solid-state battery containing the battery material.
Preparation of Battery 9
According to data listed in Table 5, raw materials A9 and B9 (the molar ratio of B9 to A9 is 0.08) and an initiator BPO are added into a solvent, the raw materials are uniformly mixed to obtain a raw material solution containing a polymer material raw material, the raw material solution is coated on the surface of a negative electrode F1, the thickness of the coating is controlled to be 2 mu m, 50 the raw material solution is used for initiating monomer in-situ polymerization to obtain a negative electrode sheet containing a polymer material coating, a positive electrode sheet C6, the negative electrode sheet containing the polymer material coating and a diaphragm S1 are laminated and baked to obtain a dry battery core, electrolyte E5 is injected into the dry battery core, the battery is packaged, and the solid battery containing the battery material is obtained by standing for 12 hours at room temperature to fully infiltrate the battery core.
Preparation of Battery 11
According to data listed in Table 5, raw materials A11 and B11 (the molar ratio of B11 to A11 is 0.75) and an initiator BPO are added into a solvent, uniformly mixed to obtain a raw material solution containing a polymer material raw material, the raw material solution is coated on the surface of a diaphragm S2, the thickness of the coating is controlled to be 2 microns, 50 the raw material solution is used for initiating in-situ polymerization of a monomer to obtain the diaphragm containing the polymer material coating, a positive pole piece C5, a negative pole piece F4 and the diaphragm containing the polymer material coating are laminated and baked to obtain a dry battery core, an electrolyte E6 is injected into the dry battery core, the battery is packaged, and the battery core is fully soaked after standing at room temperature for 12 hours to obtain the solid battery containing the battery material.
Preparation of batteries 13 and 15
Preparing a polymer material, mixing the polymer material with slurry for preparing a negative electrode F1, uniformly mixing, coating the mixture on an aluminum foil to obtain a positive plate containing the polymer material, laminating and baking the positive plate C2 containing the polymer material, the negative plate containing the polymer material and a diaphragm S1 to obtain a dry battery cell, injecting electrolyte E2 added with the battery material, packaging the battery, and standing at room temperature for 12 hours to fully infiltrate the battery cell to obtain the solid battery containing the polymer material.
Preparation of batteries 14 and 16
Preparing a polymer material, adding the polymer material into the electrolyte E3 for dissolving to obtain an electrolyte E3 containing a battery material, laminating and baking a positive pole piece, a negative pole piece and a diaphragm to obtain a dry battery core, injecting the electrolyte containing the battery material, packaging the battery, and standing at room temperature for 12 hours to fully infiltrate the battery core to obtain the solid-state battery containing the polymer material G.
Preparation of comparative batteries 14, 15
According to data listed in Table 5, in an environment with a dew point lower than-45 ℃, adding the raw material A1/A1+ B1 into an electrolyte E1, laminating and baking a positive pole piece, a negative pole piece and a diaphragm to obtain a dry battery core, injecting the electrolyte, packaging the battery, and standing at room temperature for 12 hours to fully soak the battery core to obtain the battery containing the raw material A1/A1+ B1 but without polymerization.
Wherein the amount of the initiator added into the battery is 0.2-2% of the mass of the raw materials A and B.
Table 5 example cell configuration and test mode
Wherein, D1 has the structure:
the structure of D2 is: />
The structure of K1 is:
structure of K2Comprises the following steps: />
The structure of K3 is:
7. battery testing
After the secondary battery is completely cured in situ, the first-cycle discharge capacity, the first-cycle efficiency and the capacity retention rate of the battery after 200 cycles are tested at room temperature, the test voltage range is 2.75-4.2V, wherein the cycle mode is 0.5C/0.5C 200 cycles (C represents multiplying power), and the test results are shown in Table 6.
TABLE 6 Battery test results
The invention provides a polymer material containing phosphorus groups, and the battery prepared by the in-situ curing or non-in-situ curing method greatly improves the cycling stability and safety of the battery and prolongs the service life of the battery.
As can be seen from table 6, in the battery system in which the high nickel ternary (Ni 83, NCA) and lithium cobaltate are used as the positive electrode and graphite, silicon carbon, silicon oxygen carbon and metallic lithium are used as the negative electrode, compared with the conventional lithium battery, the energy density of the battery prepared by the invention is only slightly reduced, but the cycle stability of the battery is significantly improved.
Batteries (batteries 1-12, batteries 14 and batteries 16) prepared by adopting the polymer generated by the raw materials A and B have the battery capacity of 10.25 Ah-10.68 Ah and the capacity retention rate of 92.76-94.11% after circulation for 200 weeks; the battery (comparison batteries 1-8, 13 and 15) prepared by only adopting the polymer generated by the raw material A has the battery capacity of 9.88-10.16 Ah and the capacity retention rate of 90.57-91.88% after 200 cycles; the capacity retention rate of batteries 1-12, 14 and 16 after 200 cycles is higher than that of comparative batteries 1-8, 13 and 15, which shows that the batteries prepared by introducing the polymer generated by raw materials A + B have higher cycle stability. The battery (comparison battery 9-11) prepared by only adopting the polymer generated by the raw material B has the battery capacity of 9.72-9.74 Ah and the capacity retention rate of 92.46-92.54% after 200 cycles; the capacity retention rate of the comparative batteries 9-11 after 200 cycles is higher than that of the comparative batteries 1-8, 13 and 15, which shows that the introduction of B in the invention can improve the cycle stability of the batteries. The battery (compared with batteries 12-13) prepared by only adopting the raw material D has the battery capacity of 9.12-9.22 Ah and the capacity retention ratio of 79.87% -79.96% after 200 cycles; the battery (comparative battery 14-15) prepared by adopting the raw material A or A + B without initiating in-situ curing is between 9.57 and 9.63 Ah; the capacity retention rate is 89.77-89.93% after 200 cycles; the capacity of the blank battery 1-5 is between 9.65 and 9.78Ah, and the capacity retention rate is between 84.19 and 86.91 percent after 200 cycles.
In the raw material a used in the comparative battery 1, an ester group was contained between P and the double bond; the comparative batteries 7 to 8 used the raw material A in which no ester group was present between P and the double bond. Comparing the electrochemical performances of the battery 1 and the comparative batteries 7-8 in the aspects of first effect, capacity retention rate and the like, it can be seen that the structure of the raw material A, wherein the structure of the double bond contains ester groups between P and the double bond, can enable the battery to have better electrochemical performances. The raw materials K1 and K2 used in the comparative batteries 16 to 17 had structures in which the substituents bonded to the P atom did not contain a ring structure, and the raw materials a used in the batteries 1 to 16 and the comparative batteries 1 to 8 had structures in which the substituents bonded to the P atom contained at least 1 ring structure. When the electrochemical performance of the battery is compared in the aspects of first effect, capacity retention rate and the like, it can be seen that the battery has better electrochemical performance under the condition that the substituent group connected with P in the raw material A contains a ring structure.
As can be seen from fig. 1, the capacity retention rate of the battery 1 is much higher than that of the comparative battery 12 and the blank battery 1, which indicates that the polymer material provided by the present application can significantly improve the electrochemical performance of the battery when applied to the battery.
The capacity retention of battery 1 was higher than comparative battery 1, indicating that the cyclability of the battery prepared by simultaneously introducing the polymers formed from raw materials a + B was superior to that of the battery prepared from the polymer formed from raw material a alone. The capacity retention rate of the battery 14 is slightly lower than that of the battery 1, which indicates that the battery prepared by in-situ curing has more excellent electrochemical performance, because the battery prepared by the in-situ curing method greatly improves the interface contact between the electrolyte and the pole piece, and reduces polarization and interface impedance, so that better electrical performance (such as energy density exertion, first cycle efficiency and capacity retention rate) is obtained. It can be seen from the batteries 1-14 that the present invention is suitable for various application modes, and the raw materials can be directly applied to the electrolyte, or preset in the battery assembly, or prepared into the precursor solution to be coated on the surfaces of the electrode and the diaphragm, or prepared into the polymer material to be applied to the battery. The application modes presented in the above examples are only the preferred application modes for the raw material/battery material, and other application modes of in-situ curing or non-in-situ curing can also be applicable.
Test example 2
Safety performance test of battery
And carrying out needling safety test on the prepared batteries 1-16, the comparative batteries 1-18 and the blank batteries 1-5 according to the safety requirements and the test method of the power storage battery for the electric automobile of the lithium ion battery GB-T31485-2015.
1. And (3) needle punching test: the battery is charged according to a constant current and a constant voltage of 1C, and the cut-off current is 0.05C; a high-temperature resistant steel needle with the diameter of 8mm penetrates the accumulator plate from the direction vertical to the accumulator plate at the speed of 25mm/s, the penetrating position is close to the geometric center of the punctured surface, and the steel needle stays in the accumulator; and observing for 1h, monitoring the change of the surface temperature of the battery cell in the process, and recording whether the battery cell is on fire or explodes, wherein the result is shown in a table 7.
TABLE 7 electric core acupuncture result record
The invention provides a polymer material containing a phosphorus group, which is introduced into a battery through an in-situ curing or non-in-situ curing method, so that the safety of the battery is greatly improved.
As shown in Table 7, the lithium batteries (batteries 1 to 12, 14 and 16) prepared by the polymer generated by the raw materials A and B do not fire or explode during the needling test, and the surface temperature of the battery core is 26.0-34.6 ℃ during the needling test, so that the safety of the batteries is improved; the batteries (comparative batteries 1-8, 13 and 15) prepared by only adopting the polymer generated by the raw material A have the advantages that the batteries do not fire or explode in a needling test, the surface temperature of the battery core is 40.1-49.4 ℃, and the surface temperature of the battery cores of the batteries 1-12, 14 and 16 is slightly lower than that of the comparative batteries 1-8, 13 and 15, so that the batteries prepared by simultaneously introducing the polymer generated by the raw materials A and B have higher safety. The battery (comparison battery 9-11) prepared only by the polymer generated by the raw material B is ignited and exploded when needling, and the surface temperature of the battery core is 295.2-299.1 ℃ when needling, while the battery (comparison battery 12-13) prepared only by the raw material D is ignited and exploded when needling, and the surface temperature of the battery core is 602.4-619.3 during needling; the battery (comparison battery 14-15) prepared by adopting the raw material A or A + B without initiating in-situ curing is ignited and exploded when the battery is needled, and the surface temperature of a battery core is 495.8-497.7 when the battery is needled; and 1-5 of blank batteries, the battery is ignited and exploded when being needled, and the surface temperature of the battery core is 615.3-635.0 when being needled.
In the adopted raw material A of the comparative battery 1, ester groups are contained between P and double bonds, and the surface temperature of the battery core after battery needling is 40.6 ℃; in the raw material A adopted by the comparative battery 7-8, no ester group is contained between P and the double bond, the surface temperature of the battery core after the battery is needled is respectively 49.4 ℃ and 48.7 ℃, and is higher than that of the comparative battery 1, which shows that the ester group contained between P and the double bond in the raw material A is beneficial to further improving the safety of the battery; in the raw material A adopted by the batteries 1-16 and the comparative batteries 1-8, the substituent directly connected with the P atom contains a ring structure, and the surface temperature of the battery cell after the battery needling is 26.0-49.4 ℃; compared with the raw materials K1 and K2 adopted by the batteries 16-17, the substituent directly connected with the P atom does not contain a ring structure, and the surface temperatures of the punched batteries are respectively 79.3 ℃ and 78.9 ℃, which shows that the introduction of the K1 or K2 can improve the safety of the batteries to a certain extent, but the batteries still have internal short circuit during the needling, so that the battery heating rate is higher than the heat dissipation rate, which shows that the battery heating inhibition capacity is insufficient, and further shows that the ring structure in the substituent directly connected with the P atom in the raw material A can ensure that the batteries have higher safety.
It can be seen more intuitively from fig. 2 that the battery prepared by using the polymer generated from raw material a or simultaneously introducing the polymers generated from raw materials a + B in the present invention still keeps good after needling, and the blank battery and comparative battery 12 have serious damage due to fire and explosion after needling test, which indicates that the polymer material provided by the present invention can significantly improve the safety performance of the battery when applied to the battery.
2. Test of electrical core thermal shock safety
The battery is charged according to a constant current and a constant voltage of 1C, and the current is cut off by 0.05C; heating at 180 ℃ for 2h: heating to 180 ℃ at a heating rate of 5 ℃/s, keeping the temperature for 2h, and observing for 1h; and recording whether the battery is on fire or exploded, wherein 'no fire and no explosion' are passed, otherwise, failure is caused, and monitoring the change of the surface temperature of the battery cell in the process, wherein the test result is shown in table 8.
TABLE 8 cell thermal shock safety results
The invention provides a polymer material containing a phosphorus group, and the polymer material containing the phosphorus group is introduced into a battery by an in-situ curing or non-in-situ curing method, so that the safety of the battery is greatly improved.
As shown in table 8, the batteries prepared using the polymer produced from raw material a or the polymer produced by introducing raw materials a + B at the same time all passed the thermal shock test, and the battery prepared using the polymer produced from raw material B alone, the battery containing raw material a or both raw materials a and B without polymerization, and the battery containing D1, D2 alone and the blank battery did not pass the thermal shock test. Further, the invention improves the safety of the battery.
The application introduces a polymer material containing phosphorus groups, and the safety of the battery prepared by an in-situ curing or non-in-situ curing method is greatly improved. The battery prepared by the in-situ curing method has more excellent electrochemical performance, and the interface contact between the electrolyte and the pole piece is greatly improved, and the polarization and the interface impedance are reduced, so that better electrical performance is obtained.
(3) And (3) extrusion testing: and (3) fully charging the battery, placing the battery in two planes, extruding the battery in a direction perpendicular to the polar plate at a speed of 2mm/s, and stopping extruding when the voltage reaches 0V or the battery deformation reaches 50%. The battery can pass through the extrusion process without firing or explosion.
TABLE 9 extrusion test result comparison
The invention provides a polymer material containing a phosphorus group, and the polymer material containing the phosphorus group is introduced into a battery by an in-situ curing or non-in-situ curing method, so that the safety of the battery is greatly improved.
As shown in table 9, all of the batteries prepared using the polymer produced from the raw material a or the polymer produced by introducing the raw materials a + B at the same time passed the extrusion test, the battery prepared using the polymer produced from the raw material B alone, the battery containing the raw materials a or both the raw materials a and B without polymerization, and the battery containing D1, D2 alone and the blank battery did not pass the extrusion test. Further, the invention improves the safety of the battery.
The application introduces a polymer material containing phosphorus groups, and the safety of the battery prepared by an in-situ curing or non-in-situ curing method is greatly improved. The battery prepared by the in-situ curing method has more excellent electrochemical performance, and the interface contact between the electrolyte and the pole piece is greatly improved, and the polarization and the interface impedance are reduced, so that better electrical performance is obtained.
In a needling test, a thermal shock safety test and an extrusion test, a battery prepared by adopting a polymer generated by a raw material A or simultaneously introducing a polymer generated by raw materials A and B passes the extrusion test, and a battery prepared by polymerizing the raw materials A and B has better safety and electrochemical performance, and a battery prepared by only containing the polymer generated by the raw material B, a battery containing only D1 and D2 and a blank battery do not pass the safety test. This shows that the polymer material of the present application, when used in a battery, can significantly improve the safety performance of the battery.
It should be noted that, the raw material a or the mixture of the raw material a and the raw material B in this patent may also be directly used in combination with a commercial electrolyte, and still an excellent effect may be obtained, which indicates that the raw material for preparing the polymer material in this application has a good compatibility with various electrolytes.
Raw materials which are not recorded with the preparation method in the embodiment are all the existing raw materials and can be directly purchased; the raw materials for the preparation method are described, the preparation process is the prior art, and the preparation method of the raw materials is not in the protection scope of the application, so the raw materials are not described in detail in the specification.
In conclusion, the battery prepared by the method can obviously improve the safety performance of the battery, can well maintain the electrochemical performance of the battery, and is suitable for large-scale popularization and application.
In the present invention, only a part of the structures are selected as representative examples to explain the production method, effects, and the like of the present application, and other structures not listed have similar effects.
For example, the polymeric unit- [ M ] constituting the polymer material G 1 -M 2 ]-may further comprise:
etc. R constituting the polymer material G 5 And/or R 6 The represented polymerized units may further include:
etc. other polymerization units may be so related due to space limitations and are not listed here. The polymer material structure formed by any combination of the above polymerization units is within the protection scope of the present application.
R in the above structure is H, li or BF 3 Li and A represent that any position on the ring can be substituted by a substituent such as a halogen atom, an alkyl group and the like, particularly by F, and the numerical values of m, p and n can be referred to in the summary of the invention. The terminal group in the above structure may be any group, and the present application is not limited thereto.
The polymer material structure can be obtained by combining any one, two or more of the above-mentioned polymeric units in a block, alternating or random arrangement, and these polymer material structures are also within the scope of the present application.
In the present invention, only a part of the structures are selected as representative examples to explain the preparation method, effects and the like of the present application, and other structures not listed have similar effects.
It should be noted that, the applicant has performed a great number of tests on the series of structures, and sometimes, for better comparison with the existing system, there are cases where the same structure and system are tested more than once, and therefore, there may be some error in the tests performed at different times.
Finally, it should be noted that: the above-mentioned embodiments are only used for illustrating the technical solution of the present invention, and not for limiting the same; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Unless otherwise indicated, the numerical ranges herein include not only the entire range within its two endpoints, but also several sub-ranges subsumed therein.
The preferred embodiments and examples of the present application have been described in detail with reference to the accompanying drawings, but the present application is not limited to the embodiments and examples described above, and various changes can be made within the knowledge of those skilled in the art without departing from the concept of the present application.
Claims (15)
1. A polymer material for a lithium battery, characterized in that the structure of the polymer material at least comprises [ M ] shown in formula 1 1 -M 2 ]-a polymerization unit:
wherein M is 1 Selected from C, N, P, S, si, M 2 Selected from C, O, N, P, S, si;
R 1 -R 4 independently selected from any one of no, substituent-containing or substituent-free chains or rings, in R 1 Selected from the group consisting of a substituted or unsubstituted chain, which is a pure carbon chain, or a carbon chain containing only one heteroatom;
R 5 -R 6 independently selected from any one of no, substituent-containing or substituent-free chain or ring, and polymerized unit formed based on the chain or ring, R 5 And/or R 6 Selected from- [ M ] in the case of representing polymerized units 1 -M 2 ]-polymerized units or with- [ M 1 -M 2 ]-different other polymerized units;
m is selected from 0.01-1, and represents [ M ] per 1/M 1 -M 2 ]-one of the polymerized units is present
And M 1 Or M 2 Connecting; p is selected from an integer of 10 to 10000 and represents- [ M [ ] 1 -M 2 ]The degree of polymerization of the polymerized units.
2. The polymeric material of claim 1, wherein R is 3 -R 4 Independently selected from any one of saturated carbon chain or unsaturated carbon chain consisting of no carbon atoms and 1-10 carbon atoms.
3. The polymeric material of claim 1, wherein R is 1 Contains at least one unsaturated bond and/or contains at least one heteroatom including N, O, P, S, si, F;
preferably, the unsaturated bond is = O;
more preferably, R 1 In at least one
wherein-O is either P or M 1 Directly or indirectly via chains and/or rings, -C = O and P or M 1 Directly or indirectly via chains and/or loops.
4. The polymeric material of claim 1, wherein R is 3 Is selected from
OR-OR, R is selected from any one of H, li, halogen atom, chain OR ring containing substituent OR not containing substituent;
preferably, the OR is OLi;
preferably, the substituted or unsubstituted chain or ring is a chain or ring consisting of 1 to 8 atoms;
preferably, A is 1 The substituents represented are substituted by one or more halogen atoms, preferably F, the chain containing at least one heteroatom.
5. The polymeric material of claim 1 or 4, wherein the polymeric material is a thermoplastic polymer
The cyclic structure represented by the formula (I) is selected from monocyclic ring or polycyclic ring, the monocyclic ring is selected from saturated carbocycle, saturated heterocycle, unsaturated carbocycle or unsaturated heterocycle which are three-twelve-membered, and the polycyclic ring is selected from fused ring, bridged ring, spiro ring and linked ring which are formed by combining any two monocyclic rings based on the monocyclic ring;
preferably, the monocyclic ring is selected from a five-to six-membered unsaturated carbocyclic or heterocyclic ring;
more preferably, the monocyclic ring is selected from five-six membered unsaturated heterocycles.
6. The polymeric material of claim 1,
R 5 or R 6 Is selected from [ M ] 3 -M 4 ]-polymerized units of said- [ M [ ] 3 -M 4 ]-the structure of the polymerized units is represented by formula 2:
the structure of the polymeric material is selected from:
wherein M is 3 Selected from C, N, P, S, si, M 4 Selected from C, O, N, P, S, si;
R 10 -R 14 independently selected from any one of no, substituent-containing or substituent-free chains or rings;
n is an integer of 5 to 1000 and represents [ M ] 3 -M 4 ]-the degree of polymerization of the polymeric units;
in the case of a structure of polymeric material, a single- [ M ] 1 -M 2 ]Polymerized units with a single- [ M ] 3 -M 4 ]-the polymerized units are arranged in blocks, in alternating fashion, in periodic fashion, in gradient fashion or in random fashion.
7. The polymeric material of claim 6, wherein a single- [ M ] is represented by H1 1 -M 2 ]-polymerized units
By H2 representing a single- [ M ] 3 -M 4 ]-a polymerization unit->
In the polymer material, the arrangement mode of H1 and H2 is selected from any one of the followingOne or a combination of several of:
arranged in blocks:
arranged in an alternating manner: one or more H1 s alternate with one or more H2 s in sequence;
arranged in a periodic manner: forming a plurality of periods through one or more H1 and one or more H2 respectively, wherein the plurality of periods are arranged in sequence;
arranged in a gradient fashion: the composition of H1 and H2 gradually changes along the chain;
random arrangement: one or more H1 s are arbitrarily crossed with one or more H2 s.
8. The polymeric material of claim 6, wherein R is 14 Selected from rings or chains containing at least one heteroatom, any position of which can be substituted by a substituent;
preferably, R 14 Selected from a ring or chain containing at least two heteroatoms and comprising at least one = O in the ring or chain;
more preferably, R 14 Selected from:
wherein A is 1 、A 2 Meaning that the atoms on the ring/chain can be substituted with substituents.
9. The polymeric material of claim 6, wherein the polymeric material has a structure in which m is selected from 1, p is selected from integers between 30 and 8000, n is selected from integers between 10 and 800, and p > n.
10. The polymeric material of claim 6, wherein the polymeric material is produced based on at least the reaction of a starting material a, or at least the reaction of a starting material a with a starting material B;
of starting materials AHas the structure of
The structure of the raw material B is->
11. An electrolyte comprising a polymer material according to any one of claims 1 to 10 or a raw material for producing the polymer material according to claim 10.
12. A lithium battery is characterized in that the battery comprises any one or more of the following components: the polymer material according to any one of claims 1 to 10, the raw material for producing the polymer material according to claim 10, the electrolyte according to claim 11;
the lithium battery can be a lithium ion battery or a metal lithium battery;
the lithium battery can be a liquid battery, a mixed solid-liquid battery or an all-solid-state battery; preferably, the lithium battery is a solid-state battery.
13. Use of a polymer material according to any of claims 1 to 10 in a battery, wherein the polymer material is placed in a battery component or cell of the battery, and the battery is prepared by an ex-situ curing process;
or raw materials for preparing the polymer material are placed in a battery component or a battery core of the battery, and the battery is prepared through an in-situ curing process;
wherein the battery assembly includes an electrode, a separator, and an electrolyte membrane.
14. The use of claim 13, wherein the ex situ curing of the polymeric material disposed in the cell comprises:
(1) Disposing the polymeric material in a cell of the battery, comprising:
adding the polymer material into electrolyte for dissolving, and injecting into the prepared battery cell;
(2) Disposing the polymeric material in a cell component of the battery, comprising:
dissolving the polymer material in a solvent, and then coating the polymer material on an electrode plate, a diaphragm or independently forming a film to form the electrode plate, the diaphragm or an electrolyte film with the polymer material coating; or the polymer material is blended in the positive and negative electrode slurry to form a pole piece containing the polymer material;
the in situ curing mode of placing the raw material in the battery comprises the following steps:
(1) Placing the feedstock in a cell of the battery, comprising:
adding the raw materials and an initiator into electrolyte, and forming a solid-state battery with an integrated battery core through in-situ solidification; or at least one raw material is preset in the battery assembly, an initiator and the rest raw materials are added into electrolyte, and then the electrolyte is injected into the prepared battery cell, and the solid-state battery with integrated battery cell is formed by in-situ solidification;
(2) Placing the feedstock in a cell component of the cell, comprising:
the raw materials are prepared into precursor liquid to be coated on an electrode plate, a diaphragm or a single film, and the precursor liquid is cured in situ to form the electrode plate, the diaphragm or an electrolyte film with a polymer material coating.
15. The use according to claim 14, wherein, in the case where the raw material comprises raw material A and raw material B, the molar ratio of raw material B to raw material A is 0 to 1, and the total mass of raw material A and raw material B is 1 to 50% of the total mass of the precursor solution.
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