CN114464881A - Carbon dioxide-based polycarbonate electrolyte containing abb structure, and preparation method and application thereof - Google Patents
Carbon dioxide-based polycarbonate electrolyte containing abb structure, and preparation method and application thereof Download PDFInfo
- Publication number
- CN114464881A CN114464881A CN202210130737.XA CN202210130737A CN114464881A CN 114464881 A CN114464881 A CN 114464881A CN 202210130737 A CN202210130737 A CN 202210130737A CN 114464881 A CN114464881 A CN 114464881A
- Authority
- CN
- China
- Prior art keywords
- abb
- carbon dioxide
- based polycarbonate
- electrolyte
- lithium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0065—Solid electrolytes
- H01M2300/0082—Organic polymers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0088—Composites
- H01M2300/0091—Composites in the form of mixtures
Abstract
The invention discloses a carbon dioxide-based polycarbonate electrolyte containing an abb structure, and a preparation method and application thereof, wherein the electrolyte comprises carbon dioxide-based polycarbonate containing a abb structure and lithium salt, and based on the carbon dioxide-based polycarbonate containing a abb structure and the lithium salt, the mass fraction of the polycarbonate containing a abb structure is 10-95%; the mass fraction of the lithium salt is 5-90%. The carbon dioxide-based polycarbonate containing abb structure is prepared by the copolymerization of carbon dioxide and alkylene oxide under the action of a bifunctional organic boron catalyst; abb structural unit is formed by ring-opening sequential copolymerization of carbon dioxide and two alkylene oxides. The electrolyte provided by the invention can be applied to lithium ion batteries. The invention can selectively regulate and control the composition of the polycarbonate by changing the copolymerization reaction condition, thereby realizing the regulation and control of the polymer electrolyte performance. The polymer electrolyte has the advantages of wide electrochemical window, high lithium ion conductivity and the like.
Description
Technical Field
The invention belongs to the technical field of lithium ion batteries, and particularly relates to a carbon dioxide-based polycarbonate electrolyte containing an abb structure, and a preparation method and application thereof.
Background
The lithium ion battery has the advantages of large capacity, high working voltage, high energy density, long cycle life and the like, and is widely applied to the fields of power grid energy storage, new energy automobiles and consumer electronics. However, most commercial lithium batteries adopt carbonate liquid electrolytes, and have potential safety hazards such as liquid leakage, flammability, explosion and the like. In addition, during operation of the liquid electrolyte, lithium is unevenly deposited and extracted, which causes generation of lithium dendrites, reduces cycle performance of the battery, and also pierces the separator, causing short circuit of the battery. Therefore, the development of solid electrolytes to replace the conventional liquid electrolytes has become a research and development hotspot in the front direction of lithium batteries. Compared with the defects of complex preparation process, poor interface compatibility and the like of the inorganic solid electrolyte, the polymer electrolyte has the advantages of good compatibility with lithium metal, high thermal stability, simple preparation process, good flexibility, adjustable shape and size and the like, thereby gaining wide attention.
Polyethylene oxide (PEO) has been a polymer electrolyte material of great interest since its report by Wright et al in 1973. However, the PEO-based polymer electrolyte still has many defects, such as easy crystallization, low dielectric constant, low ionic conductivity at room temperature, low electrochemical stability window, low transference number of lithium ions, substandard mechanical properties, and the like, and cannot meet the market demand. Although many researchers have physically modified (blending, plasticizers) and chemically modified (grafting, crosslinking) PEO to address these problems, they still fail to simultaneously address the above-mentioned problems. For example, Liu et al (J.Appl.Polym.Sci.2003,89, 2815-2822) by adding TiO2The nano-modified carbon nano-particles are blended with PEO in situ to explore the crystallinity and electrochemical properties of the PEO, however, the filler does not have ionic conductivity, and the nano-filler is easy to agglomerate to influence the electrolyte properties. The Chinese patent with publication number CN103500845B discloses a preparation method of a cross-linked all-solid-state polymer electrolyte material, wherein original crystallinity of PEO is reduced by adopting a cross-linked polyoxyethylene ether containing cross-linking groups to form a film, but the problems of relatively low lithium ion conductivity and poor electrochemical stability at room temperature still exist. Therefore, many scholars have been devoted to developing polymer electrolytes of novel systems.
Compared with polyether electrolyte, the polycarbonate molecular main chain has carbonate groups with stronger polarity, so that the polycarbonate molecular main chain has higher dielectric constant and is more beneficial to the dissociation of lithium salt. In addition, the carbonate group has a weaker interaction with lithium ions than the ether bond has a close interaction with lithium ions, and is more advantageous to the migration of lithium ions. However, polycarbonates have a high glass transition temperature, resulting in poor electrical conductivity. abb acts as an intermediate structure between carbonates and ethers, combining the advantages of polycarbonates and polyethers. Tremulian et al synthesized polycarbonate (electrochimica acta2017,225, 151-159) with a similar structure by using diol and carbonate as raw materials through a transesterification method, and the experimental result shows that the polycarbonate electrolyte has higher lithium ion conductivity and electrochemical window. However, the polycarbonate synthesis method requires high temperature and severe conditions (190 ℃), and by-products need to be continuously removed, which consumes a lot of energy, and in addition, the polymer melt viscosity is high in the later stage of polymerization, and the by-products are not easy to remove, which results in that the molecular weight of the synthesized polycarbonate is limited. Therefore, there is a need to develop an alternative polycarbonate synthesis route containing the abb structure.
Carbon dioxide is the main gas responsible for the greenhouse effect and is also a non-toxic, cheap, readily available renewable carbon source. Therefore, the method takes carbon dioxide as a raw material and synthesizes carbon dioxide-based polycarbonate through catalytic copolymerization with alkylene oxide, and has great prospect. For example, one U.S. patent (US 3585168) uses a two-component catalyst based on zinc alkyls to effect alternating copolymerization of carbon dioxide/propylene oxide into polycarbonate. Task groups such as Lu soldiers reported that salenCo (III) (CN 100384909C) catalyst system can realize the alternating copolymerization of carbon dioxide and oxetane to obtain polycarbonate. However, the above synthetic methods can only obtain completely alternating polycarbonate, and cannot synthesize polycarbonate containing abb structure, so that the precise regulation of the polycarbonate composition is more difficult to realize. In addition, the above-mentioned synthesis methods all involve metal catalysts, and the problem of metal residues in the polymer can seriously affect the further use of the polycarbonate.
Disclosure of Invention
The invention aims to overcome the defects of a polyether electrolyte and a polycarbonate electrolyte respectively and overcome the defects of the existing polycarbonate synthesis method, and provides a carbon dioxide-based polycarbonate electrolyte containing an abb structure, and a preparation method and application thereof. The method can selectively regulate and control the composition of the polycarbonate by changing the catalyst structure and the reaction conditions, thereby realizing the regulation and control of the polymer electrolyte performance. The electrolyte has the characteristics of wide electrochemical window and high lithium ion conductivity.
The technical scheme adopted by the invention is as follows:
a carbon dioxide-based polycarbonate electrolyte containing abb structure, the electrolyte comprises carbon dioxide-based polycarbonate containing abb structure and lithium salt, based on the carbon dioxide-based polycarbonate containing abb structure and lithium salt, the mass fraction of the carbon dioxide-based polycarbonate containing abb structure is 10% -95%; the mass fraction of the lithium salt is 5-90%, and the mass fraction of the polycarbonate containing abb structure is preferably 40-70%; the mass fraction of the lithium salt is preferably 30 to 60%.
The carbon dioxide-based polycarbonate electrolyte containing the abb structure can further contain an auxiliary agent, and the electrolyte consists of carbon dioxide-based polycarbonate containing the abb structure, lithium salt and an auxiliary agent, wherein the auxiliary agent comprises one or more of but not limited to inorganic filler, high molecular material, fast ion conductor and organic plasticizer. The mass of the auxiliary agent is 0-50% of the total mass of the carbon dioxide-based polycarbonate containing abb structure and the lithium salt. Wherein 0 can be 0, that is, the electrolyte does not contain an auxiliary agent.
Preferably, the carbon dioxide-based polycarbonate electrolyte containing abb structure consists of carbon dioxide-based polycarbonate containing abb structure and lithium salt, wherein the mass fraction of the polycarbonate containing abb structure is 10% -95%; the mass fraction of the lithium salt is 5-90%.
The carbon dioxide-based polycarbonate containing the abb structure is prepared by the following method:
under the action of a bifunctional organic boron catalyst, carbon dioxide and alkylene oxide shown in a formula I are subjected to copolymerization reaction, the carbon dioxide is used as a structural unit a, the ring opening of the alkylene oxide is used as a structural unit b and is inserted into a polymer chain, and carbon dioxide-based polycarbonate containing abb shown in a formula II is copolymerized; in the formula II, an ab structural unit represents a carbonate unit formed by ring-opening copolymerization of carbon dioxide and one alkylene oxide, an abb structural unit is formed by ring-opening sequential copolymerization of the carbon dioxide and two alkylene oxides, and a bbb structural unit represents an ether unit formed by ring-opening self-polymerization of the alkylene oxide.
The polymerization reaction formula is shown below:
in the formulae I and II, R1、R2、R3、R4Each independently hydrogen or a group selected from the following with or without substituents: c1-C30Alkyl radical, C3-C30Cycloalkyl radical, C2-C30Alkenyl radical, C3-C30Alkynyl, C6-C30Aryl or C3-C30Heterocyclyl, or said group containing one or more of the atoms O, S in the carbon chain; wherein the substituent is selected from one or more of halogen atoms, branched or straight-chain alkyl with 1 to 20 carbon atoms, branched or straight-chain alkoxy with 1 to 20 carbon atoms, ester groups with 2 to 10 carbon atoms, alkenyl with 2 to 10 carbon atoms, branched or straight-chain cycloalkyl with 3 to 20 carbon atoms, aryl with 6 to 20 carbon atoms, heterocyclic groups with 3 to 20 carbon atoms and heteroaromatic groups with 5 to 20 carbon atoms;
preferably R1、R2、R3、R4Each independently hydrogen or a group selected from the following with or without substituents: c1-C10Alkyl radical, C3-C10Cycloalkyl, C2-C10Alkenyl radical, C6-C10Aryl radicals or C3-C10Heterocyclyl, or said group containing an O atom in the carbon chain; wherein the substituent is selected from halogen atom, branched or linear alkyl with 1 to 10 carbon atoms, branched or linear alkoxy with 1 to 10 carbon atoms, ester group with 2 to 10 carbon atoms, alkenyl with 2 to 10 carbon atoms, branched or linear cycloalkyl with 3 to 10 carbon atoms, aryl with 6 to 10 carbon atoms, heterocyclic group with 3 to 10 carbon atoms, heteroaromatic with 5 to 10 carbon atomsOne or more of the groups;
said C is3-C10The heterocyclic group is preferably C3-C10Oxacycloalkyl, more preferably furyl or tetrahydrofuryl;
further, R is preferable1Is H or C1-C10Alkyl radical, R2Is H, R4Is H, R3Is C1-C10Alkyl radical, C2-C10Alkenyl or phenyl, said C1-C10Alkyl or C2-C10With or without oxygen atoms in the carbon chain of the alkenyl radical, C1-C10Alkyl radical, C2-C10H on the alkenyl or phenyl is not substituted or substituted by a substituent U, and the substituent U is halogen or C1-C10Alkoxy radical, C2-C10Alkenyl radical, C6-C10Aryl radical, C3-C10One or more of heterocyclic group and ester group; more preferably, the substituent U is halogen or C1-C10Alkoxy radical, C2-C5One or more of alkenyl, phenyl, ester, furyl, or tetrahydrofuranyl;
or R1、R3May be linked to form a ring, and together with two carbon atoms on the oxirane form C which is unsubstituted or substituted by 1 or more substituents V4-C30Cycloalkyl radical, C4-C30Cycloalkenyl radical, C4-C30Oxacycloalkyl radical, C4-C30Condensed ring radicals or C4-C30A fused ring aromatic group; the substituent V is halogen or C1-C10Alkyl radical, C1-C10Alkoxy radical, C2-C10Alkenyl or phenyl;
preferably R1、R3Linked to form a ring, and together with two carbon atoms of the oxirane forming C unsubstituted or substituted by 1 or more substituents V4-C10Cycloalkyl radical, C4-C10Cycloalkenyl radical, C4-C10Oxacycloalkyl radical, C4-C10Condensed ring radicals or C4-C10Condensed ring aromatic group, saidThe substituent V is halogen or C1-C10Alkyl radical, C1-C10Alkoxy radical, C2-C10Alkenyl or phenyl;
R1、R3when joined to form a ring, R2、R4Preferably each independently of the other is H or C1-C10An alkyl group.
R1、R3The cyclic group formed by the linkage to form a ring can be represented by ring Q, and the reaction formula can be represented by the following formula
Formula I' represents R1、R3The formula I and the formula II' which are connected to form a ring represent R1、R3In the formula II 'and II', the ring Q represents R1、R3Linking the resulting cyclic group;
further, it is preferable that the Q ring is one of:
wherein Z represents O, N, S, C1-C20C containing one or more oxygen, nitrogen or sulfur atoms in alkylene or carbon chain1-C20An alkylene group; z is preferably O, N, S, C1-C5C containing one or more oxygen, nitrogen or sulfur atoms in alkylene or carbon chain1-C5An alkylene group;
h on ring Q is unsubstituted or substituted with 1 or more substituents V; the substituent V is halogen or C1-C10Alkyl radical, C1-C10Alkoxy radical, C2-C10Alkenyl or phenyl;
in the formula II, x represents the number of carbonate units, y represents the number of abb structural units, z represents the number of ether units, and x, y and z are independently selected from any integer of 0-100000, wherein y can not be 0.
Further, x is preferably an integer of 1 to 10000, y is preferably an integer of 1 to 8000, and z is preferably an integer of 0 to 20000.
In the method, the chemical formula of the bifunctional organoboron catalyst is one or more of the following:
wherein N is a nitrogen atom and B is a boron atom;
each K1、K2Independently selected from the following groups with or without substituents: c1-C30Alkyl radical, C3-C30Cycloalkyl radical, C3-C30Alkenyl or C6-C30An aromatic group or the group containing one or more of O, S, silicon and nitrogen atoms in a carbon chain; wherein the substituent is selected from one or more of halogen atoms, branched or straight-chain alkyl with 1 to 20 carbon atoms, branched or straight-chain alkoxy with 1 to 20 carbon atoms, branched or straight-chain cycloalkyl with 3 to 20 carbon atoms, aryl with 6 to 20 carbon atoms, heterocyclic radical with 3 to 20 carbon atoms and heteroaromatic radical with 5 to 20 carbon atoms;
or B, K1、K2Linked to form a boron-containing cycloalkyl;
each R5、R6、R7Independently selected from the group consisting of: c1-C30Alkyl radical, C3-C30Cycloalkyl radical, C3-C30Alkenyl or C6-C30Aryl, preferably C1-C10An alkyl group; wherein each R is5、R6、R7Two or more of them may be linked to the N atom to form a ring, thereby forming a nitrogen-containing heterocyclic group;
each Y is1、Y2、Y3、Y4Is independently selected from C1-C30Alkylene, preferably C1-C10An alkylene group;
X-represents a negative ion; x-Exists in the form of single negative ion; said X is-Is selected from F-、Cl-、Br-、I-、OH-、NO3 -、N3 -、BF4 -、(C6F5)4B-Sulfonate, perchlorate, chlorate, phosphate, carboxylate, alkoxide or phenoxide.
The bifunctional organoboron catalysts are disclosed in J.Am.chem.Soc.2021,143,9, 3455-3465, and can be synthesized by methods referred to therein.
Preferably, each of the bifunctional organoboron catalyst structures
Each independently represented as one of:
each m and n is independently selected from any integer of 0 to 18, preferably 0 to 10.
More preferably, the bifunctional organoboron catalyst is of one or more of the following chemical formula:
preferably, the alkylene oxide of formula I is one or more of the following:
more preferably, the alkylene oxide shown in the formula I is propylene oxide, and the chemical structure of the carbon dioxide based polypropylene carbonate containing abb structure obtained by copolymerizing the propylene oxide and carbon dioxide is shown as the following formula II-1:
in the formula II-1, x represents the number of carbonate units, y represents the number of abb structural units, z represents the number of ether units, x, y and z are independently selected from any integer of 0-100000, and y cannot be 0. Preferably, x is an integer of 5 to 10000, preferably y is an integer of 5 to 8000, and preferably z is an integer of 0 to 20000.
Preferably, in the copolymerization reaction, the reaction temperature is 0-150 ℃, and more preferably 25-90 ℃; the pressure of the carbon dioxide is 0.1-10.0 MPa, and more preferably 0.5-2.5 MPa; the reaction time is 0.1-72 h, and more preferably 0.3-12 h; the mass ratio of the bifunctional organoboron catalyst to the alkylene oxide is 1: 200 to 200000, and preferably 1:1000 to 10000.
After the copolymerization reaction is finished, the reaction product is subjected to post-treatment to obtain the carbon dioxide-based polycarbonate containing the abb structure, and the reaction solution is subjected to post-treatment, namely the reaction product is dissolved by using dichloromethane and then precipitated by using a hydrochloric acid methanol solution to remove impurities, so that the carbon dioxide-based polycarbonate containing the abb structure is obtained.
In the carbon dioxide-based polycarbonate containing abb structure, the connection mode of ab, abb and bbb structural units is one or more of random, block and gradient. The carbon dioxide-based polycarbonate containing the abb structure has the number average molecular weight of 500-5000000 Da and the molecular weight distribution of 1.00-10.00. The mole fraction of abb structural units in the carbon dioxide-based polycarbonate containing abb structure is 1-100%, preferably 1-99%.
Further, in the carbon dioxide-based polycarbonate electrolyte having the abb structure, the lithium salt is preferably selected from one or more of lithium perchlorate, lithium hexafluorophosphate, lithium difluorophosphate, lithium bis (oxalato) borate, lithium difluorooxalato borate, lithium tetrafluoroborate, boric dimalonate, lithium malonato oxalato borate, lithium hexafluoroarsenate, lithium trifluoromethanesulfonate, lithium bistrifluoromethanesulfonylimide, lithium bistrifluoromethanesulfonylmethylsulfonylmethylide, lithium 4, 5-dicyano-2-trifluoromethylimidazole, and is preferably selected from lithium bistrifluoromethanesulfonylimide, lithium bis (oxalato) borate, and lithium trifluoromethanesulfonate.
The invention also provides a preparation method of the carbon dioxide-based polycarbonate electrolyte containing the abb structure, which comprises the following steps: uniformly mixing and dissolving carbon dioxide-based polycarbonate containing abb structure and an organic solvent to obtain a uniform polycarbonate solution; adding lithium salt into the polycarbonate solution, adding the auxiliary agent when the auxiliary agent exists in the raw materials, and continuously and uniformly stirring to obtain a mixed solution; pouring the mixed solution into a flat plate mold, and drying in vacuum to obtain the carbon dioxide-based polycarbonate electrolyte containing the abb structure.
Based on the carbon dioxide-based polycarbonate containing abb structure and lithium salt, wherein the mass fraction of the polycarbonate containing abb structure is 10-95%; the mass fraction of the lithium salt is 5-90%.
Preferably, the organic solvent is one or a mixture of two or more of acetonitrile, dimethyl sulfoxide, sulfolane, dimethyl sulfite, diethyl sulfite, acetone, tetrahydrofuran, toluene, dichloromethane, chloroform, ethyl acetate, N-dimethylformamide and N, N-dimethylacetamide, and preferably tetrahydrofuran, N-dimethylformamide or chloroform.
The volume dosage of the organic solvent is generally 5-15 mL/g based on the mass of the carbon dioxide-based polycarbonate containing abb structure.
The flat mold is typically a teflon mold.
The invention also provides a carbon dioxide-based polycarbonate electrolyte containing a plurality of abb structures, which comprises carbon dioxide-based polycarbonate containing a plurality of abb structures and lithium salt, wherein the mass fraction of the polycarbonate containing a plurality of abb structures is 10-95% based on the carbon dioxide-based polycarbonate containing a plurality of abb structures and the lithium salt; the mass fraction of the lithium salt is 5-90%. Based on the carbon dioxide-based polycarbonate containing various abb structures and lithium salt, the mass fraction of the polycarbonate containing various abb structures is preferably 40-70%; the mass fraction of the lithium salt is preferably 30 to 60%.
The carbon dioxide-based polycarbonate electrolyte containing various abb structures can further contain an auxiliary agent, and the carbon dioxide-based polycarbonate electrolyte containing various abb structures is composed of carbon dioxide-based polycarbonate containing various abb structures, lithium salt and an auxiliary agent, wherein the auxiliary agent comprises one or more of but not limited to inorganic filler, high molecular material, fast ion conductor and organic plasticizer. The mass of the auxiliary agent is 0-50% of the total mass of the carbon dioxide-based polycarbonate containing various abb structures and the lithium salt. Wherein 0 can be 0, that is, the electrolyte does not contain an auxiliary agent.
Preferably, the carbon dioxide-based polycarbonate electrolyte containing various abb structures consists of carbon dioxide-based polycarbonate containing various abb structures and lithium salt, wherein the mass fraction of the polycarbonate containing various abb structures is 10-95%; the mass fraction of the lithium salt is 5-90%.
In the carbon dioxide-based polycarbonate electrolyte containing various abb structures, the definition of lithium salt is as described above.
The carbon dioxide-based polycarbonate containing various abb structures is prepared by the following method: the carbon dioxide and more than two types of alkylene oxides are subjected to copolymerization reaction to prepare the carbon dioxide-based polycarbonate containing various abb structures, and the specific method comprises the following steps: under the action of a bifunctional organic boron catalyst, carbon dioxide and n different types of alkylene oxides shown in formula I are subjected to copolymerization reaction, wherein the carbon dioxide is used as a structural unit a, and a plurality of alkylene oxides are respectively subjected to ring opening to be used as a structural unit b1、b2、……、bnInserting polymer chains, and copolymerizing to form the carbon dioxide-based polycarbonate containing various abb structures; knots in the productThe structural units comprise carbonate units, abb structural units and ether units, the carbonate units comprise carbon dioxide and one alkylene oxide ring-opening copolymerization formed ab1、ab2、……、abnOne or more of the units, abb structural unit comprising carbon dioxide and two alkylene oxides ring-opening sequentially copolymerized to form ab1b1、ab2b2、ab1b2、…、abpbq、…、abnbnOne or more of the units; the ether unit comprises b formed by ring-opening self-polymerization of alkylene oxide1b1b1、b2b2b2、b1b1b2、…、brbtbs、…、bnbnbnOne or more of the units.
b1、b2、……、bnRespectively represent structural units of n alkylene oxide raw materials after ring opening;
n represents the number of the raw materials of the alkylene oxide participating in the copolymerization reaction, and n is an integer of 2-5.
abpbqWherein p and q are each independently an integer of 1 to n;
brbtbswherein r, t and s are each independently an integer of 1 to n.
Carbonate unit ab1、ab2、……、abnThe number of repeating units of each unit may be x1、x2、……、xnDenotes x1、x2、……、xnEach independently is an integer of 0 to 100000; preferably, each is an integer of 0 to 10000 independently;
abb structural element ab1b1、ab2b2、ab1b2、…、abpbq、…、abnbnThe number of repeating units of each unit may be y11、y22、y12、…、ypq、…、ynnDenotes y11、y22、y12、…、ypq、…、ynnEach independently is an integer of 0 to 100000, but not both; preferably, each independently is an integer of 0 to 10000, but not both are 0;
ether unit b1b1b1、b2b2b2、b1b1b2、…、brbtbs、…、bnbnbnThe number of repeating units of each unit may be represented by z111、z222、z112、…、zrts、…、znnnIs represented by z111、z222、z112、…、zrts、…、znnnEach independently is an integer of 0 to 100000, preferably 0 to 20000.
The bifunctional organoboron catalyst and the alkylene oxide shown in the formula I are defined as before, and the conditions of the copolymerization reaction are also described as before.
When carbon dioxide and a plurality of alkylene oxides are copolymerized, the composition of each structural unit in the polycarbonate can be selectively regulated and controlled by adjusting the reaction conditions and the catalyst structure, when more than two types of alkylene oxides are involved in the reaction, the structural unit after ring opening, the carbon dioxide and the alkylene oxides self-polymerize, and a great number of combination modes exist, but in fact, the carbonate unit, abb structural unit or ether unit in the product may not contain all combinations, for example, in the embodiment 5 of the invention, propylene oxide, cyclohexene oxide and carbon dioxide react, wherein the cyclohexene oxide completely generates the polycarbonate, so that abb and polyether structures do not exist.
In the carbon dioxide-based polycarbonate containing a plurality of abb structures, the connection mode of each structural unit is one or more of random, block and gradient. The carbon dioxide-based polycarbonate containing various abb structures has the number average molecular weight of 500-5000000 Da and the molecular weight distribution of 1.00-10.00. The mole fraction of abb structural units in the carbon dioxide-based polycarbonate containing various abb structures is 1-100%, preferably 1-99%.
The preparation method of the carbon dioxide-based polycarbonate electrolyte containing various abb structures comprises the following steps: uniformly mixing and dissolving carbon dioxide-based polycarbonate containing various abb structures and an organic solvent to obtain a uniform polycarbonate solution; adding lithium salt into the polycarbonate solution, adding the auxiliary agent when the auxiliary agent exists in the raw materials, and continuously and uniformly stirring to obtain a mixed solution; pouring the mixed solution into a flat plate mold, and drying in vacuum to obtain the carbon dioxide-based polycarbonate electrolyte containing the abb structure.
The carbon dioxide-based polycarbonate electrolyte containing the abb structure can be applied to the field of lithium ion batteries.
The carbon dioxide-based polycarbonate electrolyte containing various abb structures can be applied to the field of lithium ion batteries.
Compared with the prior art, the invention has the beneficial effects that: the polycarbonate preparation method adopted by the invention takes the main gas carbon dioxide causing the greenhouse effect as the raw material to synthesize the carbon dioxide-based polycarbonate containing abb structure and the carbon dioxide-based polycarbonate containing a plurality of abb structures, and has the advantages of atom economy, no metal, controllable polymerization product and the like. And mixing the carbon dioxide-based polycarbonate containing abb structures or carbon dioxide-based polycarbonate containing multiple abb structures, lithium salt and an auxiliary agent to prepare the polymer electrolyte, wherein the electrolyte can be applied to a lithium ion battery. By changing one or more polymerization reaction conditions such as catalyst structure, catalyst/alkylene oxide ratio, reaction temperature, carbon dioxide pressure, reaction time and the like, the proportions of carbonate units, abb structural units and ether units in the polycarbonate composition can be accurately regulated, so that the advantages of both polyether and polycarbonate electrolyte are reasonably utilized, and the regulation and control of the performance of the polymer electrolyte are realized. The carbon dioxide-based polycarbonate electrolyte containing the abb structure has the advantages of wide electrochemical window and high lithium ion conductivity.
Drawings
FIG. 1 is a nuclear magnetic hydrogen spectrum of the polypropylene carbonate containing abb structure of example 1.
FIG. 2 is a nuclear magnetic hydrogen spectrum of the polypropylene carbonate containing abb structure in example 2.
FIG. 3 is a comparison of DSC curves of the polypropylene carbonates of different proportions of constituent units in examples 1 and 2.
Fig. 4 is a diagram showing an electrochemical window of a polypropylene carbonate electrolyte containing abb structure prepared in example 2.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be further described in detail with reference to the accompanying drawings and examples. It should be understood that the detailed description and specific examples, while indicating the scope of the invention, are intended for purposes of illustration only and are not intended to limit the scope of the invention.
In the present invention, the catalyst is synthesized according to the method disclosed in J.Am.chem.Soc.2021,143,9, 3455-3465.
Specifically, the catalyst 1 is synthesized by the following method:
in a glove box, 40mL of tetrahydrofuran solution (0.5mol/L) containing the raw material 1 and 2.48g of the raw material 2(0.01mol) are reacted for 6h at 60 ℃, the solvent tetrahydrofuran is pumped out, and the tetrahydrofuran is washed by hexane to obtain the target product catalyst 1.
The catalyst 2 was synthesized as follows:
in a glove box, 80mL of tetrahydrofuran solution (0.5mol/L) containing the raw material 1 and 2.58g of the raw material 3(0.01mol) are taken to react for 12h at 60 ℃, the solvent tetrahydrofuran is pumped out, and the tetrahydrofuran is washed by hexane to obtain the target product catalyst 2.
The catalyst 3 was synthesized as follows:
in a glove box, 20mL of tetrahydrofuran solution (0.5mol/L) containing the raw material 1 and 1.80g of the raw material 4(0.01mol) are reacted at 60 ℃ for 6h, the solvent tetrahydrofuran is pumped out, and the tetrahydrofuran is washed by hexane to obtain the target product catalyst 3.
in a glove box, 3.56g of raw material 5(0.02mol) and 2.48g of raw material 2(0.01mol) were taken, 50mL of tetrahydrofuran was added as a solvent, the reaction was carried out at 60 ℃ for 6 hours, the solvent tetrahydrofuran was drained, and the reaction product was washed with hexane to obtain the objective catalyst 4.
The catalyst 5 was synthesized as follows:
in a glove box, 0.84g of raw material 6(0.02mol) and 2.48g of raw material 2(0.01mol) were taken, 50mL of tetrahydrofuran was added as a solvent, the reaction was carried out at 60 ℃ for 6 hours, the solvent tetrahydrofuran was drained, and the reaction product was washed with hexane to obtain the objective catalyst 5.
The catalyst 6 was synthesized as follows:
taking 6.92g of raw material 7(0.02mol) and 2.48g of raw material 2(0.01mol) in a glove box, adding 50mL of tetrahydrofuran as a solvent, reacting at 60 ℃ for 6h, draining the solvent tetrahydrofuran, and washing with hexane to obtain the target product catalyst 6.
Example 1
The synthesis method of the carbon dioxide based polypropylene carbonate containing the abb structure comprises the following steps:
the catalyst 1 has the following structural formula:
purified propylene oxide (3g, 51.7mmol) and catalyst 1(25.6mg, 0.052mmol) were added to an autoclave under anhydrous and oxygen-free conditions, charged with carbon dioxide (2.0MPa), and reacted at 40 ℃ for 6 h. Dissolving the product with dichloromethane, precipitating with hydrochloric acid methanol solution to remove impurities such as catalyst and the like, and obtaining the following carbon dioxide based polypropylene carbonate containing abb structure:
the nuclear magnetic hydrogen spectrum result shows that the polycarbonate contains 91.2 percent of carbonate units, 8.2 percent of abb structural units and 0.5 percent of ether units (molar ratio).
1g of the polypropylene carbonate and 8g of tetrahydrofuran are added into a 50mL reagent bottle and stirred for 2 hours at 40 ℃ to obtain a uniform polypropylene carbonate solution. 0.5g of lithium bistrifluoromethanesulfonylimide was added to the above polypropylene carbonate solution, and stirred at room temperature for 2 hours to obtain a uniform mixed solution. Then pouring the mixture into a polytetrafluoroethylene mold, and drying the mixture in a vacuum oven at 40 ℃ for 24 hours to obtain the carbon dioxide-based polypropylene carbonate electrolyte containing abb structures.
Example 2
The synthesis method of the carbon dioxide based polypropylene carbonate containing the abb structure comprises the following steps:
purified propylene oxide (3g, 51.7mmol) and catalyst 1(25.6mg, 0.052mmol) were added to an autoclave under anhydrous and oxygen-free conditions, charged with carbon dioxide (1.0MPa), and reacted at 90 ℃ for 0.3 h. Dissolving the product with dichloromethane, precipitating with hydrochloric acid methanol solution to remove impurities such as catalyst and the like, and obtaining the following carbon dioxide based polypropylene carbonate containing abb structure:
the results of nuclear magnetic hydrogen spectroscopy show that the polycarbonate contains 57.8% of carbonate units, 36.4% of abb structural units and 5.8% of ether units (molar ratio).
1g of the polypropylene carbonate and 8g of tetrahydrofuran are added into a 50mL reagent bottle and stirred for 2 hours at 40 ℃ to obtain a uniform polypropylene carbonate solution. 0.5g of lithium bistrifluoromethanesulfonylimide was added to the above polypropylene carbonate solution, and stirred at room temperature for 2 hours to obtain a uniform mixed solution. Then pouring the mixture into a polytetrafluoroethylene mold, and drying the mixture in a vacuum oven at 40 ℃ for 24 hours to obtain the carbon dioxide-based polypropylene carbonate electrolyte containing abb structures.
Example 3
The synthesis method of the carbon dioxide based polypropylene carbonate containing the abb structure comprises the following steps:
the catalyst 2 has the following structural formula:
purified propylene oxide (3g, 51.7mmol) and catalyst 2(38.8mg, 0.052mmol) were added to an autoclave in the absence of water and oxygen, charged with carbon dioxide (2.0MPa) and reacted at 40 ℃ for 6 h. Dissolving the product with dichloromethane, precipitating with hydrochloric acid methanol solution to remove impurities such as catalyst and the like, and obtaining the following carbon dioxide based polypropylene carbonate containing abb structure:
the results of nuclear magnetic hydrogen spectroscopy show that the polycarbonate contains 69.7% of carbonate units, 21.4% of abb structural units and 8.9% of ether units (molar ratio).
1g of the polypropylene carbonate and 8g of tetrahydrofuran are added into a 50mL reagent bottle and stirred for 2 hours at 40 ℃ to obtain a uniform polypropylene carbonate solution. 0.5g of lithium bistrifluoromethanesulfonylimide was added to the above polypropylene carbonate solution, and stirred at room temperature for 2 hours to obtain a uniform mixed solution. Then pouring the mixture into a polytetrafluoroethylene mold, and drying the mixture in a vacuum oven at 40 ℃ for 24 hours to obtain the carbon dioxide-based polypropylene carbonate electrolyte containing abb structures.
Example 4
The synthesis method of the carbon dioxide based polycyclohexene carbonate containing abb structure comprises the following steps:
the catalyst 3 has the following structural formula:
purified cyclohexene oxide (3g, 30.6mmol) and catalyst 3(5.2mg, 0.015mmol) were added to an autoclave under anhydrous and oxygen-free conditions, charged with carbon dioxide (0.5MPa) and reacted at 80 ℃ for 3 h. Dissolving the product with dichloromethane, precipitating with hydrochloric acid methanol solution to remove impurities such as catalyst, and obtaining the following carbon dioxide-based polycyclohexene carbonate containing abb structure:
the results of nuclear magnetic hydrogen spectroscopy showed that the polycarbonate had a carbonate unit content of 76.7%, a abb structural unit content of 21.6%, and an ether unit content of 1.7% (molar ratio).
1g of the polycyclohexene carbonate and 8g of N, N-dimethylformamide are added into a 50mL reagent bottle and stirred for 2 hours at 40 ℃ to obtain a uniform polycyclohexene carbonate solution. 1.5g of lithium bis (oxalato) borate was added to the above polycyclohexene carbonate solution, and stirred at room temperature for 2 hours to obtain a uniform mixed solution. Then pouring the mixture into a polytetrafluoroethylene mold, and drying the mixture in a vacuum oven at 60 ℃ for 24 hours to obtain the carbon dioxide-based polycyclohexene carbonate electrolyte containing abb structures.
Example 5
The synthesis method of the carbon dioxide based polypropylene carbonate-cyclohexene ester copolymer containing the abb structure comprises the following steps:
purified propylene oxide (2g,34.4mmol), cyclohexene oxide (1.7g, 17.2mmol) and catalyst 1(16.7mg, 0.034mmol) were charged to an autoclave in the absence of water and oxygen, charged with carbon dioxide (1.5MPa) and reacted at 60 ℃ for 3 h. Dissolving the product by using dichloromethane, precipitating by using a hydrochloric acid methanol solution to remove impurities such as a catalyst and the like, and obtaining the following carbon dioxide based polypropylene carbonate-cyclohexene ester copolymer containing abb structure:
the results of nuclear magnetic hydrogen spectroscopy showed that the above-mentioned polypropylene-cyclohexene carbonate copolymer contained 70.3% of carbonate units, 23.9% of abb structural units and 5.8% of ether units (molar ratio).
1g of the above-mentioned polypropylene-cyclohexene carbonate copolymer and 8g of tetrahydrofuran were put into a 50mL reagent bottle and stirred at 40 ℃ for 2 hours to obtain a uniform polypropylene-cyclohexene carbonate copolymer solution. 1g of lithium trifluoromethanesulfonate was added to the above-mentioned polypropylene-cyclohexene carbonate copolymer solution, and stirred at room temperature for 2 hours to obtain a uniform mixed solution. Then pouring the mixture into a polytetrafluoroethylene mold, and drying the mixture in a vacuum oven at 40 ℃ for 48 hours to obtain the carbon dioxide-based polypropylene carbonate-cyclohexene ester copolymer electrolyte containing abb structures.
Example 6
The synthesis method of the carbon dioxide based polypropylene carbonate-chloropropene ester copolymer containing the abb structure comprises the following steps:
the purified propylene oxide PO (2g,34.4mmol), epichlorohydrin ECH (1.6g, 17.2mmol) and catalyst 2(25.4mg, 0.034mmol) were charged into an autoclave under anhydrous and oxygen-free conditions, charged with carbon dioxide (2.5MPa), and reacted at 60 ℃ for 4 h. Dissolving the product with dichloromethane, precipitating with hydrochloric acid methanol solution to remove impurities such as catalyst, and obtaining the following carbon dioxide based polypropylene carbonate-chloropropene ester copolymer containing abb structure:
the nuclear magnetic hydrogen spectrum result shows that the polycarbonate-chloropropene ester copolymer contains 90.2 percent of carbonate units, 3.3 percent of abb structural units and 6.5 percent of ether units (molar ratio).
1g of the polypropylene carbonate-chloropropene ester copolymer and 8g of chloroform are added into a 50mL reagent bottle and stirred for 2 hours at room temperature to obtain a uniform polypropylene carbonate-chloropropene ester copolymer solution. 1g of lithium trifluoromethanesulfonate was added to the above polypropylene-chloropropene carbonate copolymer solution, and stirred at room temperature for 2 hours to obtain a uniform mixed solution. Then pouring the mixture into a polytetrafluoroethylene mold, and drying the mixture in a vacuum oven at 40 ℃ for 48 hours to obtain the carbon dioxide based polypropylene carbonate-chloropropylene ester copolymer electrolyte containing abb structure.
Example 7
The synthesis method of the carbon dioxide based polypropylene carbonate containing the abb structure comprises the following steps:
the catalyst 4 has the following structural formula:
the purified propylene oxide PO (3g, 51.7mmol) and catalyst 4(31.4mg, 0.052mmol) were added to an autoclave under anhydrous and oxygen-free conditions, charged with carbon dioxide (2.0MPa), and reacted at 40 ℃ for 6 h. Dissolving the product with dichloromethane, precipitating with hydrochloric acid methanol solution to remove impurities such as catalyst and the like, and obtaining the following carbon dioxide based polypropylene carbonate containing abb structure:
the results of nuclear magnetic hydrogen spectroscopy show that the polycarbonate contains 82.1% of carbonate units, 15.3% of abb structural units and 2.6% of ether units (molar ratio).
1g of the polypropylene carbonate and 8g of tetrahydrofuran are added into a 50mL reagent bottle and stirred for 2 hours at 40 ℃ to obtain a uniform polypropylene carbonate solution. 0.5g of lithium bistrifluoromethanesulfonylimide was added to the above polypropylene carbonate solution, and stirred at room temperature for 2 hours to obtain a uniform mixed solution. Then pouring the mixture into a polytetrafluoroethylene mold, and drying the mixture in a vacuum oven at 40 ℃ for 24 hours to obtain the carbon dioxide-based polypropylene carbonate electrolyte containing abb structures.
Example 8
The synthesis method of the carbon dioxide based polypropylene carbonate containing the abb structure comprises the following steps:
the catalyst 5 has the following structural formula:
the purified propylene oxide PO (3g, 51.7mmol) and catalyst 5(17.3mg, 0.052mmol) were added to an autoclave under anhydrous and oxygen-free conditions, charged with carbon dioxide (2.0MPa), and reacted at 40 ℃ for 6 h. Dissolving the product with dichloromethane, precipitating with hydrochloric acid methanol solution to remove impurities such as catalyst and the like, and obtaining the following carbon dioxide based polypropylene carbonate containing abb structure:
the results of nuclear magnetic hydrogen spectroscopy show that the polycarbonate contains 63.4% of carbonate units, 31.7% of abb structural units and 4.9% of ether units (molar ratio).
1g of the polypropylene carbonate and 8g of tetrahydrofuran are added into a 50mL reagent bottle and stirred for 2 hours at 40 ℃ to obtain a uniform polypropylene carbonate solution. 0.5g of lithium bistrifluoromethanesulfonylimide was added to the above polypropylene carbonate solution, and stirred at room temperature for 2 hours to obtain a uniform mixed solution. Then pouring the mixture into a polytetrafluoroethylene mold, and drying the mixture in a vacuum oven at 40 ℃ for 24 hours to obtain the carbon dioxide-based polypropylene carbonate electrolyte containing abb structures.
Example 9
The synthesis method of the carbon dioxide based polypropylene carbonate containing the abb structure comprises the following steps:
the catalyst 6 has the following structural formula:
the purified propylene oxide PO (3g, 51.7mmol) and catalyst 6(48.9mg, 0.052mmol) were added to an autoclave under anhydrous and oxygen-free conditions, charged with carbon dioxide (2.0MPa), and reacted at 40 ℃ for 6 h. Dissolving the product with dichloromethane, precipitating with hydrochloric acid methanol solution to remove impurities such as catalyst and the like, and obtaining the following carbon dioxide based polypropylene carbonate containing abb structure:
the nuclear magnetic hydrogen spectrum result shows that the polycarbonate contains 93.4 percent of carbonate units, 6.3 percent of abb structural units and 0.3 percent of ether units (molar ratio).
1g of the polypropylene carbonate and 8g of tetrahydrofuran are added into a 50mL reagent bottle and stirred for 2 hours at 40 ℃ to obtain a uniform polypropylene carbonate solution. 0.5g of lithium bistrifluoromethanesulfonylimide was added to the above polypropylene carbonate solution, and stirred at room temperature for 2 hours to obtain a uniform mixed solution. Then pouring the mixture into a polytetrafluoroethylene mold, and drying the mixture in a vacuum oven at 40 ℃ for 24 hours to obtain the carbon dioxide-based polypropylene carbonate electrolyte containing abb structures.
Example 10
The synthesis method of the carbon dioxide-based poly (styrene carbonate) containing abb structure comprises the following steps:
purified styrene oxide SO (6.2g, 51.7mmol) and catalyst 2(38.8mg, 0.052mmol) were added to an autoclave under anhydrous and oxygen-free conditions, charged with carbon dioxide (0.5MPa), and reacted at 40 ℃ for 12 h. Dissolving the product with dichloromethane, precipitating with hydrochloric acid methanol solution to remove impurities such as catalyst, and obtaining the following carbon dioxide-based poly (styrene carbonate) containing abb structure:
the results of nuclear magnetic hydrogen spectroscopy showed that the above-mentioned polystyrene carbonate had 28.1% of carbonate units, 45.4% of abb structural units and 26.5% of ether units (molar ratio).
1g of the above-mentioned poly (styrene carbonate) and 8g of tetrahydrofuran were put into a 50mL reagent bottle and stirred at 40 ℃ for 2 hours to obtain a uniform poly (styrene carbonate) solution. 0.5g of lithium bistrifluoromethanesulfonylimide was added to the above-mentioned styrene polycarbonate solution, and stirred at room temperature for 2 hours to obtain a uniform mixed solution. Then pouring the mixture into a polytetrafluoroethylene mold, and drying the mixture in a vacuum oven at 40 ℃ for 24 hours to obtain the carbon dioxide-based poly (styrene carbonate) electrolyte containing abb structures.
Example 11
The synthesis method of the carbon dioxide based poly allyl glycidyl carbonate containing abb structure comprises the following steps:
purified allyl glycidyl ether AGE (5.9g, 51.7mmol) and catalyst 2(38.8mg, 0.052mmol) were added to an autoclave under anhydrous and oxygen-free conditions, charged with carbon dioxide (2.0MPa), and reacted at 40 ℃ for 6 h. Dissolving the product with dichloromethane, precipitating with hydrochloric acid methanol solution to remove impurities such as catalyst, and obtaining the following carbon dioxide based poly (allyl glycidyl carbonate) containing abb structure:
the results of nuclear magnetic hydrogen spectroscopy showed that the above polyallyl glycidyl carbonate had a carbonate unit content of 70.3%, abb structural units content of 26.7%, and an ether unit content of 3.0% (molar ratio).
1g of the above polyallyl glycidyl carbonate and 8g of tetrahydrofuran were put into a 50mL reagent bottle and stirred at 40 ℃ for 2 hours to obtain a uniform polyallyl glycidyl carbonate solution. 0.5g of lithium bistrifluoromethanesulfonylimide was added to the above allyl glycidyl polycarbonate solution, and stirred at room temperature for 2 hours to obtain a uniform mixed solution. Then pouring the mixture into a polytetrafluoroethylene mold, and drying the mixture in a vacuum oven at 40 ℃ for 24 hours to obtain the carbon dioxide-based poly (allyl glycidyl carbonate) electrolyte containing abb structures.
Example 12
The synthesis method of the carbon dioxide-based polycarbonate limonene ester containing the abb structure comprises the following steps:
purified limonene oxide LO (7.9g, 51.7mmol), catalyst 2(38.8mg, 0.052mmol) were added to an autoclave under anhydrous and oxygen-free conditions, charged with carbon dioxide (2.0MPa), and reacted at 25 ℃ for 8 h. Dissolving the product with dichloromethane, and precipitating with hydrochloric acid methanol solution to remove impurities such as catalyst, to obtain the following carbon dioxide-based polycarbonate limonene ester containing abb structure:
the results of nuclear magnetic hydrogen spectroscopy showed that the above polycarbonate limonene ester contained 87.1% of carbonate units, 11.2% of abb structural units and 1.7% of ether units (molar ratio).
1g of the above-mentioned limonene polycarbonate and 8g of tetrahydrofuran were put into a 50mL reagent bottle and stirred at 40 ℃ for 2 hours to obtain a uniform limonene polycarbonate solution. 0.5g of lithium bistrifluoromethanesulfonylimide was added to the above limonene polycarbonate solution, and stirred at room temperature for 2 hours to obtain a uniform mixed solution. Then pouring the mixture into a polytetrafluoroethylene mold, and drying the mixture in a vacuum oven at 40 ℃ for 24 hours to obtain the carbon dioxide-based polycarbonate limonene ester electrolyte containing abb structures.
The test results of the polymerization products of examples 1 to 12 are shown in Table 1 below.
Table 1 test results for the polymerization products of examples 1-12:
Mn 1: number average molecular weight, as determined by gel permeation chromatography; PDI2: molecular weight distribution of gelAnd (4) measuring by using a permeation chromatography method.
The properties of the polycarbonate solid electrolytes prepared in examples 1 to 12 were characterized as follows:
thickness of electrolyte: the thickness of the polymer electrolyte was measured using a micrometer (precision 0.01 mm), and 3 points on any sample were measured and averaged.
Ionic conductivity: the electrolyte was clamped with two pieces of stainless steel, and the impedance was measured for the button cell of 2032 assembled, using the formula: where L is the thickness of the electrolyte, a is the room temperature area of the stainless steel sheet, and R is the measured impedance.
Electrochemical window: a polymer electrolyte is clamped by stainless steel and a lithium sheet, a 2032 button cell is assembled, and linear volt-ampere scanning measurement is carried out, wherein the initial voltage is 0V, the highest potential is 6V, and the scanning speed is 1 mV/s.
The electrochemical window of the polycarbonate solid electrolyte prepared in example 2 is shown in fig. 4.
The results of the performance tests of the electrolytes obtained in examples 1 to 12 are shown in Table 2.
TABLE 2
From the results in Table 2, it is understood that the room temperature ionic conductivity and electrochemical window of the electrolytes prepared in examples 1 to 12 are substantially better than those of the conventional polyethylene oxide electrolyte (1.35X 10)-5S/cm). The conductivity of the polymer electrolytes prepared in examples 1 to 12 was measured, and most of the examples had ion conductivity close to that of the application (10)-4S/cm) and the electrochemical window is more than 4.6V, which proves that the invention catalytically copolymerizes the alkylene oxide and the carbon dioxide through the optimized polymerization condition to obtain the carbon dioxide-based polycarbonate containing abb structure, and can effectively improve the room temperature ions of the prepared polymer electrolyte.
Claims (13)
1. The carbon dioxide-based polycarbonate electrolyte containing abb structure is characterized in that the electrolyte comprises carbon dioxide-based polycarbonate containing abb structure and lithium salt, and the mass fraction of the carbon dioxide-based polycarbonate containing abb structure is 10-95% based on the carbon dioxide-based polycarbonate containing abb structure and the lithium salt; the mass fraction of the lithium salt is 5-90%.
2. The abb-containing carbon dioxide-based polycarbonate electrolyte according to claim 1, wherein the abb-containing carbon dioxide-based polycarbonate electrolyte comprises abb-containing carbon dioxide-based polycarbonate, lithium salt, and an auxiliary agent, wherein the auxiliary agent is one or more of a filler, a polymer material, a fast ion conductor, and an organic plasticizer; the mass of the auxiliary agent is 0-50% of the total mass of the carbon dioxide-based polycarbonate containing abb structure and the lithium salt; wherein 0 can be 0, that is, the electrolyte does not contain an auxiliary agent.
3. The carbon dioxide-based polycarbonate electrolyte containing abb structure according to claim 1, wherein the carbon dioxide-based polycarbonate electrolyte containing abb structure is composed of a carbon dioxide-based polycarbonate containing abb structure and a lithium salt, wherein the mass fraction of the polycarbonate containing abb structure is 10% to 95%; the mass fraction of the lithium salt is 5-90%.
4. The carbon dioxide-based polycarbonate electrolyte containing abb structural elements according to any of claims 1-3, wherein the carbon dioxide-based polycarbonate containing abb structural elements is prepared by the following method:
under the action of a bifunctional organic boron catalyst, carbon dioxide and alkylene oxide shown in the formula I are subjected to copolymerization reaction, the carbon dioxide is used as a structural unit a, the ring opening of the alkylene oxide is used as a structural unit b and is inserted into a polymer chain, and carbon dioxide-based polycarbonate containing abb structure shown in the formula II is copolymerized; in the formula II, an ab structural unit represents a carbonate unit formed by ring-opening copolymerization of carbon dioxide and one alkylene oxide, an abb structural unit is formed by ring-opening sequential copolymerization of the carbon dioxide and two alkylene oxides, and a bbb structural unit represents an ether unit formed by ring-opening self-polymerization of the alkylene oxide;
the polymerization reaction formula is shown below:
in the formulae I and II, R1、R2、R3、R4Each independently hydrogen or a group selected from the following with or without substituents: c1-C30Alkyl radical, C3-C30Cycloalkyl radical, C2-C30Alkenyl radical, C3-C30Alkynyl, C6-C30Aryl or C3-C30Heterocyclyl, or said group containing one or more of the atoms O, S in the carbon chain; wherein the substituent is selected from one or more of halogen atoms, branched or straight-chain alkyl with 1 to 20 carbon atoms, branched or straight-chain alkoxy with 1 to 20 carbon atoms, ester groups with 2 to 10 carbon atoms, alkenyl with 2 to 10 carbon atoms, branched or straight-chain cycloalkyl with 3 to 20 carbon atoms, aryl with 6 to 20 carbon atoms, heterocyclic groups with 3 to 20 carbon atoms and heteroaromatic groups with 5 to 20 carbon atoms;
or R1、R3Linked to form a ring, and together with two carbon atoms of the oxirane forming C unsubstituted or substituted by 1 or more substituents V4-C30Cycloalkyl radical, C4-C30Cycloalkenyl radical, C4-C30Oxacycloalkyl radical, C4-C30Condensed ring radicals or C4-C30A fused ring aromatic group; the substituent V is halogen or C1-C10Alkyl radical, C1-C10Alkoxy radical, C2-C10Alkenyl or phenyl;
in the formula II, x represents the number of carbonate units, y represents the number of abb structural units, z represents the number of ether units, and x, y and z are independently selected from any integer of 0-100000, wherein y can not be 0.
5. The abb-containing carbon dioxide-based polycarbonate electrolyte of claim 4, wherein the bifunctional organoboron catalyst has a chemical formula of one or more of:
wherein N is a nitrogen atom and B is a boron atom;
each K1、K2Independently selected from the following groups with or without substituents: c1-C30Alkyl radical, C3-C30Cycloalkyl radical, C3-C30Alkenyl or C6-C30An aromatic group or the group containing one or more of O, S, silicon and nitrogen atoms in a carbon chain; wherein the substituent is selected from one or more of halogen atoms, branched or straight-chain alkyl with 1 to 20 carbon atoms, branched or straight-chain alkoxy with 1 to 20 carbon atoms, branched or straight-chain cycloalkyl with 3 to 20 carbon atoms, aryl with 6 to 20 carbon atoms, heterocyclic radical with 3 to 20 carbon atoms and heteroaromatic radical with 5 to 20 carbon atoms;
or B, K1、K2Linked to form a boron-containing cycloalkyl;
each R5、R6、R7Independently selected from the group consisting of: c1-C30Alkyl radical, C3-C30Cycloalkyl radical, C3-C30Alkenyl or C6-C30Aryl, or each R5、R6、R7Two or more of them and N atom are connected to form a ring to form a nitrogen-containing heterocyclic group;
each Y is1、Y2、Y3、Y4Is independently selected from C1-C30An alkylene group;
X-represents a negative ion;X-exists in the form of single negative ion; said X-Is selected from F-、Cl-、Br-、I-、OH-、NO3 -、N3 -、BF4 -、(C6F5)4B-Sulfonate, perchlorate, chlorate, phosphate, carboxylate, alkoxide or phenoxide.
6. The abb-containing carbon dioxide-based polycarbonate electrolyte according to claim 4, wherein the alkylene oxide of formula I is one of the following:
7. the carbon dioxide-based polycarbonate electrolyte with abb structure according to claim 4, wherein in the carbon dioxide-based polycarbonate with abb structure, the ab, abb and bbb structural units are linked in one or more of random, block and gradient; the carbon dioxide-based polycarbonate containing the abb structure has the number average molecular weight of 500-5000000 Da and the molecular weight distribution of 1.00-10.00; the mole fraction of abb structural units in the carbon dioxide-based polycarbonate containing abb structure is 1-100%.
8. The abb-containing carbon dioxide-based polycarbonate electrolyte as claimed in any one of claims 1 to 3, wherein the lithium salt is one or more selected from lithium perchlorate, lithium hexafluorophosphate, lithium difluorophosphate, lithium bis (oxalato) borate, lithium difluoro (oxalato) borate, lithium tetrafluoroborate, bis (malonato) borate, lithium malonato oxalato borate, lithium hexafluoroarsenate, lithium trifluoromethanesulfonate, lithium bistrifluoromethanesulfonylimide, lithium bistrifluoromethanesulfonylmethylsulphide, and lithium 4, 5-dicyano-2-trifluoromethylimidazole.
9. The method for preparing the abb-containing carbon dioxide-based polycarbonate electrolyte according to any one of claims 1-8, wherein the method comprises: uniformly mixing and dissolving carbon dioxide-based polycarbonate containing abb structure and an organic solvent to obtain a uniform polycarbonate solution; adding lithium salt into the polycarbonate solution, adding the auxiliary agent when the auxiliary agent exists in the raw materials, and continuously stirring and uniformly mixing to obtain a mixed solution; pouring the mixed solution into a flat plate mold, and drying in vacuum to obtain the carbon dioxide-based polycarbonate electrolyte containing the abb structure.
10. The use of the abb-containing carbon dioxide-based polycarbonate electrolyte according to any one of claims 1-8 in a lithium ion battery.
11. A carbon dioxide-based polycarbonate electrolyte containing a plurality of abb structures, which is characterized in that the carbon dioxide-based polycarbonate electrolyte containing a plurality of abb structures comprises carbon dioxide-based polycarbonate containing a plurality of abb structures and lithium salt, wherein the mass fraction of the polycarbonate containing a plurality of abb structures is 10-95% based on the carbon dioxide-based polycarbonate containing a plurality of abb structures and the lithium salt; the mass fraction of the lithium salt is 5-90 percent;
the carbon dioxide-based polycarbonate containing various abb structures is prepared by the following method: the carbon dioxide and more than two types of alkylene oxides are subjected to copolymerization reaction to prepare the carbon dioxide-based polycarbonate containing various abb structures, and the specific method comprises the following steps: under the action of a bifunctional organic boron catalyst, carbon dioxide and n different types of alkylene oxides shown in formula I are subjected to copolymerization reaction, wherein the carbon dioxide is used as a structural unit a, and a plurality of alkylene oxides are respectively subjected to ring opening to be used as a structural unit b1、b2、……、bnInserting polymer chains, and copolymerizing to form the carbon dioxide-based polycarbonate containing various abb structures; the structural units in the product comprise carbonate units, abb structural units and ether units, the carbonate units comprise carbon dioxide and one alkylene oxide ring-opening copolymerized to form ab1、ab2、……、abnOne or more of the units, abb structural unit comprises carbon dioxide and twoAb formed by ring-opening sequential copolymerisation of alkylene oxides1b1、ab2b2、ab1b2、…、abpbq、…、abnbnOne or more of the units; the ether unit comprises b formed by ring-opening self-polymerization of alkylene oxide1b1b1、b2b2b2、b1b1b2、…、brbtbs、…、bnbnbnOne or more of the units;
b1、b2、……、bnrespectively represent structural units of n alkylene oxide raw materials after ring opening;
n represents the number of the raw materials of the alkylene oxide participating in the copolymerization reaction, and n is an integer of 2-5;
abpbqwherein p and q are each independently an integer of 1 to n;
brbtbswherein r, t and s are each independently an integer of 1 to n;
carbonate unit ab1、ab2、……、abnThe number of repeating units of each unit is x1、x2、……、xnDenotes x1、x2、……、xnEach independently is an integer of 0 to 100000;
abb structural element ab1b1、ab2b2、ab1b2、…、abpbq、…、abnbnThe number of repeating units of each unit is y11、y22、y12、…、ypq、…、ynnDenotes y11、y22、y12、…、ypq、…、ynnEach independently is an integer of 0 to 100000, but not both;
ether unit b1b1b1、b2b2b2、b1b1b2、…、brbtbs、…、bnbnbnThe number of repeating units of each unit is represented by z111、z222、z112、…、zrts、…、znnnIs represented by z111、z222、z112、…、zrts、…、znnnEach independently is an integer of 0 to 100000;
in the formula I, R1、R2、R3、R4Each independently hydrogen or a group selected from the following with or without substituents: c1-C30Alkyl radical, C3-C30Cycloalkyl, C2-C30Alkenyl radical, C3-C30Alkynyl, C6-C30Aryl or C3-C30Heterocyclyl, or said group containing one or more of the atoms O, S in the carbon chain; wherein the substituent is selected from one or more of halogen atoms, branched or straight-chain alkyl with 1 to 20 carbon atoms, branched or straight-chain alkoxy with 1 to 20 carbon atoms, ester groups with 2 to 10 carbon atoms, alkenyl with 2 to 10 carbon atoms, branched or straight-chain cycloalkyl with 3 to 20 carbon atoms, aryl with 6 to 20 carbon atoms, heterocyclic groups with 3 to 20 carbon atoms and heteroaromatic groups with 5 to 20 carbon atoms;
or R1、R3Linked to form a ring, and together with two carbon atoms on the oxirane forming C unsubstituted or substituted by 1 or more substituents V4-C30Cycloalkyl radical, C4-C30Cycloalkenyl radical, C4-C30Oxacycloalkyl radical, C4-C30Condensed ring radicals or C4-C30A fused ring aromatic group; the substituent V is halogen or C1-C10Alkyl radical, C1-C10Alkoxy radical, C2-C10Alkenyl or phenyl.
12. The carbon dioxide-based polycarbonate electrolyte with multiple abb structures according to claim 11, wherein the carbon dioxide-based polycarbonate electrolyte with multiple abb structures contains additives, and the carbon dioxide-based polycarbonate electrolyte with multiple abb structures is composed of carbon dioxide-based polycarbonate with multiple abb structures, lithium salt and additives, and the additives are one or more of inorganic fillers, high molecular materials, fast ion conductors and organic plasticizers; the mass of the auxiliary agent is 0-50% of the total mass of the carbon dioxide-based polycarbonate containing various abb structures and the lithium salt, wherein 0 can be 0, namely the electrolyte does not contain the auxiliary agent.
13. Use of the carbon dioxide-based polycarbonate electrolyte comprising a plurality of structures abb of claim 11 or 12 in a lithium ion battery.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210130737.XA CN114464881A (en) | 2022-02-12 | 2022-02-12 | Carbon dioxide-based polycarbonate electrolyte containing abb structure, and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210130737.XA CN114464881A (en) | 2022-02-12 | 2022-02-12 | Carbon dioxide-based polycarbonate electrolyte containing abb structure, and preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN114464881A true CN114464881A (en) | 2022-05-10 |
Family
ID=81413994
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210130737.XA Pending CN114464881A (en) | 2022-02-12 | 2022-02-12 | Carbon dioxide-based polycarbonate electrolyte containing abb structure, and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114464881A (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20180051134A1 (en) * | 2015-06-15 | 2018-02-22 | King Abdullah University Of Science And Technology | Copolymerization of carbon dioxide and cyclic monomers to form polycarbonates |
| CN112390819A (en) * | 2019-08-19 | 2021-02-23 | 浙江大学 | Organic catalyst, preparation method and application |
| CN113451640A (en) * | 2020-03-25 | 2021-09-28 | 浙江大学 | Polycarbonate-based self-gel polymer electrolyte and preparation method and application thereof |
-
2022
- 2022-02-12 CN CN202210130737.XA patent/CN114464881A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20180051134A1 (en) * | 2015-06-15 | 2018-02-22 | King Abdullah University Of Science And Technology | Copolymerization of carbon dioxide and cyclic monomers to form polycarbonates |
| CN112390819A (en) * | 2019-08-19 | 2021-02-23 | 浙江大学 | Organic catalyst, preparation method and application |
| CN113451640A (en) * | 2020-03-25 | 2021-09-28 | 浙江大学 | Polycarbonate-based self-gel polymer electrolyte and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Ballard et al. | Ionic conductivity in organic solids derived from amorphous macromolecules | |
| US7504473B2 (en) | Conductive polymeric compositions for lithium batteries | |
| US9056944B2 (en) | Ductile polymer binders and battery components using the same | |
| CN110563938B (en) | Polyether copolymer, crosslinkable polyether copolymer composition, electrolyte, and composite | |
| KR100718861B1 (en) | Composition for battery electrolyte, and polymer electrolyte and polymer battery prepared therefrom | |
| CN116053575A (en) | Carbon dioxide-based terpolymer electrolyte and preparation method and application thereof | |
| CN109755643B (en) | Oxygen-enriched polymer electrolyte and preparation method and application thereof | |
| Ye et al. | Polymer electrolytes as solid solvents and their applications | |
| CN113451640B (en) | Polycarbonate-based self-gel polymer electrolyte and preparation method and application thereof | |
| CN112358624A (en) | Polymer electrolyte capable of working in wide temperature range and preparation method thereof | |
| CN114464881A (en) | Carbon dioxide-based polycarbonate electrolyte containing abb structure, and preparation method and application thereof | |
| CN111934006B (en) | Intrinsically microporous polyaluminum/borate solid electrolytes and batteries | |
| CN116231060A (en) | Preparation method and application of single lithium ion conductive fluoropolymer solid electrolyte | |
| CA2320953A1 (en) | Polymeric compounds, polymers for polymer electrolytes, and ion-conductive polymer electrolyte compositions | |
| KR20010037163A (en) | Heat-Crosslinkable Polysiloxane Electrolytes Composition And Method For Preparing Solid Polymer Electrolytic Film By Using The Same | |
| CN117558975B (en) | Aza-addition polyether ester group all-solid polymer electrolyte and preparation method and application thereof | |
| Sanchez et al. | Polymer and salt selection for lithium polymer batteries | |
| CN112072170B (en) | Polyaluminium/borate solid electrolyte and battery | |
| Arcana et al. | Preparation of polymers electrolyte membranes from styrofoam waste for lithium battery | |
| KR100313560B1 (en) | Graft solid polymer electrolyte and its manufacturing method | |
| CN104892803B (en) | A kind of branched XNBR of borate compounds and its preparation method and application | |
| CN116979140A (en) | Carbon dioxide-based polycyclic carbonate electrolyte and preparation method and application thereof | |
| JPH04301370A (en) | High molecular solid electrolyte | |
| WO2023175341A1 (en) | New polymers for battery applications | |
| Tominaga | A New Class of Ion-Conductive Polymer Electrolytes: CO2/Epoxide Alternating Copolymers With Lithium Salts |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |