CN111934006A - Intrinsically microporous polyaluminum/borate solid electrolytes and batteries - Google Patents
Intrinsically microporous polyaluminum/borate solid electrolytes and batteries Download PDFInfo
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Abstract
The invention discloses an inherent microporous polyaluminium/borate solid electrolyte and a battery, wherein the inherent microporous polyaluminium/borate solid electrolyte is an alkali metal salt of a coordination compound formed by at least one ligand Ar and a coordination atom M, and the structural formula of the ligand Ar is shown in the specification
At least one ligand Ar is a non-centrosymmetric structure, and the structural formula of the polyaluminium/borate solid electrolyte is shown in the specification
Wherein N represents an alkali metal element, N represents a degree of polymerization, and X represents1、X2Each independently selected from SO2CO or absent, Y is selected from
And Y isSelected from-OH, -COOH, -SO3At least 2 substitutions of substituents in H. The non-centrosymmetric ligand is adopted, the structure of the polyaluminium/borate solid electrolyte formed by the ligand is a highly twisted one-dimensional molecular chain, and the molecular chain cannot be tightly stacked in a three-dimensional space, so that inherent micropores are formed, the performance improvement in multiple aspects can be realized by introducing the inherent micropores, and the non-centrosymmetric ligand has a better application prospect in the field of batteries.
Description
Technical Field
The present invention relates to solid electrolytes, and more particularly to an inherently microporous polyaluminium/borate solid electrolyte and battery.
Background
Lithium ion batteries are widely used in smart phones, notebook computers, and electric vehicles due to their excellent properties such as high energy density, long life, and high voltage. With the development of smart phones and notebook computers, such as light weight, thinness, multifunctionality, and large screen, and electric vehicles, the requirements for energy density and safety of batteries are increasing. However, over the last thirty years, the energy density of conventional lithium ion batteries based on liquid electrolytes and intercalation compounds has approached their limits and the space for lift is very limited. Moreover, the conventional liquid electrolyte contains a large amount of combustible solvent, and can cause serious safety problems such as deflagration and even explosion under abnormal conditions.
In order to further improve the energy density and safety of lithium ion batteries, the preparation of all-solid-state lithium ion batteries (ASSLIB) using solid-state electrolytes (SSE) is one of the solutions. ASSLIB has no flammable liquid solvent, so that the inherent safety of ASSLIB is higher than that of a traditional liquid electrolyte lithium ion battery, and at least no electrolyte leakage accident occurs. And because no liquid solvent exists, the packaging requirement of ASSLIB is correspondingly lower than that of the traditional liquid electrolyte lithium ion battery, so that the weight proportion of the packaging material in the battery can be reduced, and the energy density of the battery can be improved through phase transformation. Moreover, the SSE has a wide electrochemical stability window, which may exceed 5V, so that ASSLIB can adopt a lithium metal negative electrode with higher specific capacity and more negative potential, and the positive electrode can adopt LiNi with a voltage platform close to 5V0.5Mn1.5O4And the same high voltage positive electrode material, thereby improving the energy density of the battery.
The organic solid electrolyte has the advantages of easy molding, easy formation of good interface contact and the like, and becomes one of the research hotspots, wherein the transference number of lithium ions of the single lithium ion conduction solid polymer electrolyte (SLIC-SPE) is close to 1, and the problems of concentration polarization and the like caused by anion accumulation are avoided, so that the SLIC-SPE can perform in the battery enough to be equal to 10 times of the conductivityThe above dual-ion solid electrolyte has attracted much attention. SLIC-SPE refers to SPE in which anions are fixed on a macromolecular skeleton and cannot move, and only lithium ions migrate in a polymer matrix, and the conduction current of the SPE is almost completely borne by the lithium ions. SLIC-SPEs fall into a wide variety of categories, the most common SLIC-SPEs refer to an anion covalently immobilized on a polymer backbone, which anion can be grafted onto or directly present in the backbone. The anion in such SLIC-SPE is usually sulfonimide anion (-SO)2N(－)SO2-) and their derivatives and tetra-coordinated boron/aluminate anions, etc. Wherein the negative charge of the sulfonimide anion can be delocalized over four oxygens and one nitrogen, and thus becomes the most interesting solid electrolyte. However, compared with the four-coordination boric acid/aluminate anions, the sulfonimide anions are difficult to synthesize, so that the synthesis process cost is increased. The tetra-coordinated boric acid/aluminate negative ion has wide research prospect due to the advantages of easily obtained synthetic raw materials, simple process, high thermal stability and the like.
However, the reported tetra-coordinated borate/aluminate anions have insufficient negative charge delocalization and high corresponding lithium ion dissociation energy due to the fact that the adopted ligands are ligands with weak electron-withdrawing ability such as pentaerythritol, tartaric acid and the like, wherein even lithium tartrate borate with low dissociation energy has the dissociation energy of up to 146kcal/mol, and the high dissociation energy means low ionic conductivity.
Disclosure of Invention
The present invention is directed to solving at least one of the problems of the prior art. Therefore, the invention provides the inherent microporous polyaluminium/borate solid electrolyte and the battery, compared with the conventional lithium polyborate, the solid electrolyte can obviously reduce the dissociation energy of lithium ions so as to improve the conductivity of the lithium ions.
The technical scheme adopted by the invention is as follows:
in a first aspect of the invention, there is provided an inherently microporous polyaluminium/borate solid electrolyte which is an alkali metal salt of a coordination compound formed by at least one ligand Ar and a coordinating atom M, wherein the ligand Ar has the formula
At least one ligand Ar is a non-centrosymmetric structure, and the structural formula of the inherent microporous polyaluminium/borate solid electrolyte is shown in the specification
Wherein M represents boron or aluminum, N represents an alkali metal element, N represents a degree of polymerization, and X represents1、X2Each independently selected from SO2CO or absent, Y is selected from
And Y is selected from-OH, -COOH, -SO3At least 2 substituents of H.
n represents the degree of polymerization and can be adjusted according to the ratio of the raw materials added. In some embodiments, n is an integer selected from 1 to 10000. In some embodiments, n is an integer selected from 100 to 10000.
According to some embodiments of the invention, the ligand Ar is selected from
According to some embodiments of the invention, the ligand Ar and the coordinating atom M can form a five-membered ring, a six-membered ring or a seven-membered ring.
According to some embodiments of the invention, the ligand Ar forms MO with the coordinating atom M2C2Five-membered ring, MO2C3Six-membered ring, MO2SC2Six-membered rings or MO2C4A seven-membered ring.
According to some embodiments of the invention, the intrinsically microporous polyaluminium/borate solid state electrolyte is selected from
According to some embodiments of the invention, the alkali metal element is any one of lithium, sodium, and potassium.
In a second aspect of the present invention, there is provided a process for the preparation of the above-described inherently microporous polyaluminium/borate solid state electrolyte, comprising the steps of:
and adding the ligand Ar, boric acid or aluminum hydroxide and alkali into a polar solvent, stirring for reaction, and evaporating to obtain the inherent microporous polyaluminium/borate solid electrolyte.
Examples of the base to be added in the above-mentioned production step include lithium hydroxide, sodium hydroxide, potassium hydroxide and the like.
According to some embodiments of the invention, the polar solvent comprises water or a polar organic solvent.
According to some embodiments of the invention, the polar organic solvent is selected from any one of methanol, ethanol, N-methylpyrrolidone, dimethylsulfoxide, N-dimethylformamide.
In a third aspect of the invention, there is provided a battery comprising an inherently microporous polyaluminium/borate solid state electrolyte as described above.
The embodiment of the invention has the beneficial effects that:
the embodiment of the invention provides an inherent microporous polyaluminium/borate solid electrolyte, wherein a conjugated benzene ring ligand with strong electron-withdrawing capability is selected, so that negative charges of anions are delocalized to the whole main chain, lithium ions are favorably migrated along the main chain, the lithium ion dissociation energy is reduced, and the lithium ion conductivity is improved. Meanwhile, a non-centrosymmetric ligand is adopted, the structure of the formed polyaluminium/borate solid electrolyte is a highly twisted one-dimensional molecular chain, and the molecular chain cannot be tightly stacked in a three-dimensional space, so that inherent micropores are formed.
The introduction of inherent micropores in inherent micropore polyaluminium/borate solid electrolyte (abbreviated as PLAIM/PLBIM) realizes the improvement of various performances. First, the inherent microporosity improves the solubility of the polyaluminum/lithium borate in that the solvents that can dissolve the pliim/PLBIM are more numerous and more soluble. The solubility is a necessary condition for preparing an electrolyte membrane by adopting a solution casting method, and the biggest advantage that the organic solid electrolyte is easy to form is reserved due to the solubility of the PLAIM/PLBIM. Second, the introduction of intrinsic micropores increases the ionic conductivity. Third, the incorporation of intrinsic micropores suppresses crystallization of PLAIM/PLBIM and phase separation problems during film formation. When the PLAIM/PLBIM is mixed with a flexible matrix (such as PEO and the like) to form a membrane, on one hand, the rigid twisted chain segments of the PLAIM/PLBIM prevent the crystallization of the PLAIM/PLBIM, and on the other hand, the inherent micropores can contain PEO and inhibit the crystallization of PEO, so that the influence of the crystallization of PEO on the conductivity of lithium ion is relieved, and the ion conductivity is effectively improved.
Drawings
Fig. 1 is a molecular structure and three-dimensional configuration diagram of solid electrolytes of example 1 and comparative example 1;
fig. 2 is a molecular structure and three-dimensional configuration diagram of solid electrolytes of example 5 and comparative example 2;
fig. 3 is a diagram showing the molecular structure and three-dimensional configuration of the solid electrolytes of example 7 and comparative example 3.
Detailed Description
The concept and technical effects of the present invention will be clearly and completely described below in conjunction with the embodiments to fully understand the objects, features and effects of the present invention. It is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments, and those skilled in the art can obtain other embodiments without inventive effort based on the embodiments of the present invention, and all embodiments are within the protection scope of the present invention.
Example 1
This example provides a solid electrolyte of lithium poly (2, 3-dihydroxy-1, 4-benzenedicarboxylate borate), (
M is boron atom) according to the following steps:
to 200 g of dimethyl sulfoxide was added 19.80 g of 2, 3-dihydroxy-1, 4-benzenedicarboxylic acid
6.183 g of boric acid and 4.196 g of lithium hydroxide monohydrate are stirred and reacted for 6 hours at room temperature to obtain a pale yellow solution, and the pale yellow solution is subjected to rotary evaporation to obtain the lithium poly-2, 3-dihydroxy-1, 4-phthalate borate.
Structural characterization: the 13C nmr spectra showed formants at chemical shifts of 113.7, 118.0, 143.6 and 156.6ppm, corresponding to carbon on the benzene ring linked to the carboxyl group, carbon on the benzene ring linked to hydrogen, carbon on the benzene ring linked to the straight chain of hydroxyl groups, and carbon on the carboxyl group, respectively. The analysis result of the carbon, hydrogen and nitrogen elements is C: 45.15% and polymer formula (C)8O6BLi) n corresponds to a close theoretical carbon content (45.28%) and thus, the structural correctness of the resulting lithium poly-2, 3-dihydroxy-1, 4-benzenedicarboxylate borate is demonstrated.
Calculating dissociation energy: adopting a density functional method, and simulating a prepared poly-2, 3-dihydroxy-1, 4-phthalic acid lithium borate structure by Gaussian09 (Vision B.01) software, wherein MO is formed by a ligand and a boron atom2C3Six-membered ring, calculating lithium ion dissociation energy E from optimized configurationd(EdEqual to the anion energy plus the lithium ion energy minus the lithium salt energy), wherein B3LYP/6-31+ G (d) is adopted as the optimized configuration, B3LYP/6-311+ G (2df) is adopted as the energy of the optimized configuration, and the dissociation energy of the lithium poly-2, 3-dihydroxy-1, 4-phthalate borate is calculated to be 117 kcal/mol.
Comparative example 1: comparative example 1 use of a centrosymmetric ligand 2, 5-dihydroxyterephthalic acid
Synthesizing a solid electrolyte of the lithium polyborate according to the following steps: adding 19.80 g of 2, 5-dihydroxy terephthalic acid, 6.183 g of boric acid and 4.196 g of lithium hydroxide monohydrate into 200 g of dimethyl sulfoxide, stirring and reacting for 6 hours at room temperature to obtain a light yellow solution, and performing rotary evaporation to obtain the lithium polyborate solid electrolyte.
Simulating the three-dimensional molecular configurations of the lithium poly-2, 3-dihydroxy-1, 4-benzenedicarboxylate borate prepared in example 1 and the lithium polyborate solid electrolyte prepared in comparative example 1 by using gaussian software, simulating the accumulation of molecular chains in a three-dimensional space by using a molecular fragment containing 6 repeating units and taking a benzene ring as a terminal group as a structural model, the molecular structure fragment and the three-dimensional configuration schematic diagram are shown in figure 1, wherein white spheres, gray spheres, red spheres, pink spheres, yellow spheres and purple spheres represent hydrogen, carbon, oxygen, boron, sulfur and lithium ions respectively, while comparative example 1 uses a centrosymmetric ligand to form a linear polymer (as shown in a of fig. 1), example 1 uses a non-centrosymmetric ligand to form a structural segment that is highly twisted and cannot be densely packed in three-dimensional space, thereby forming intrinsic micropores (as shown in B of fig. 1).
In the prior art, when polyaluminium acid/lithium borate is used as a solid electrolyte alone, the problems of poor film forming performance, low ionic conductivity and the like exist, and in order to improve the problems, the polyaluminium acid/lithium borate is usually required to be blended with some flexible polymers to form a composite film, wherein common flexible polymers comprise polyethylene oxide (PEO), polyvinylidene fluoride (PVDF), tetrafluoroethylene-hexafluoropropylene copolymer (PTFE-HFP) and the like. However, the solid electrolyte has poor compatibility with these flexible polymers, and there are problems such as crystallization and phase separation during film formation, and it is difficult to form a solid electrolyte membrane having a uniform molecular level. The inherent micropore polyaluminium/borate solid electrolyte provided by the embodiment of the invention has no problems of crystallization, phase separation and the like when being compounded with a substrate such as PEO and the like to form a film due to the introduction of the inherent micropore, and can form a solid electrolyte film with uniform molecular level by adopting a simple solution mixing method, thereby having obvious advantages.
Example 2
This example provides a lithium poly (2, 3-dihydroxy-1, 4-benzenedicarboxylate) aluminate solid electrolyte
M is aluminum atom) according to the following steps:
to 200 g of dimethyl sulfoxide was added 19.80 g of 2, 3-dihydroxy-1, 4-benzenedicarboxylic acid
7.800 g of aluminum hydroxide and 4.196 g of lithium hydroxide monohydrate are stirred and reacted for 6 hours at 100 ℃ to obtain light yellow solution, and the light yellow solution is rotated and evaporated to obtain poly 2, 3-dihydroxyLithium aluminate 1, 4-benzenedicarboxylate.
Structural characterization: the 13C nmr spectra showed formants at chemical shifts 118.4, 143.9, and 175.8ppm, corresponding to the benzene ring carbon, the benzene ring carbon that is linear with the hydroxyl group, and the carboxyl group carbon, respectively. The analysis result of the carbon, hydrogen and nitrogen elements is C: 42.05% and polymer formula (C)8O6The theoretical carbon content (42.11%) corresponding to AlLi) n is close, thus proving that the structure of the obtained lithium aluminate poly-2, 3-dihydroxy-1, 4-benzenedicarboxylate is correct.
Calculating dissociation energy: adopting a density functional method, simulating the prepared poly-2, 3-dihydroxy-1, 4-phthalic acid lithium aluminum acid structure by Gaussian09 (Vision B.01) software, wherein MO is formed by a ligand and an aluminum atom2C3Six-membered ring, calculating lithium ion dissociation energy E from optimized configurationd(EdEqual to the anion energy plus the lithium ion energy minus the lithium salt energy), wherein B3LYP/6-31+ G (d) is adopted as the optimized configuration, B3LYP/6-311+ G (2df) is adopted as the energy of the optimized configuration, and the dissociation energy of the poly-2, 3-dihydroxy-1, 4-phthalic acid lithium aluminate is calculated to be 121 kcal/mol.
Example 3
This example provides a solid electrolyte of lithium poly (3, 6-dihydroxy-1, 2-benzenedicarboxylate borate), (
M is boron atom) according to the following steps:
to 200 g of dimethyl sulfoxide was added 19.80 g of 3, 6-dihydroxy-1, 2-benzenedicarboxylic acid
6.183 g of boric acid and 4.196 g of lithium hydroxide monohydrate are stirred and reacted for 6 hours at room temperature to obtain a pale yellow solution, and the pale yellow solution is subjected to rotary evaporation to obtain the lithium poly-3, 6-dihydroxy-1, 2-phthalate borate.
Structural characterization: the 13C nuclear magnetic resonance spectrum shows formants at chemical shifts of 108.2, 124.4, 149.9 and 162.7ppm, corresponding to carbon linked to carboxyl on the benzene ring, carbon linked to hydrogen on the benzene ring, carbon linked to a straight chain of hydroxyl on the benzene ring, and carboxyl carbon, respectively. Carbon hydrogen nitrogenThe elemental analysis result was C: 45.15% and polymer formula (C)8O6BLi) n corresponds to a close theoretical carbon content (45.28%) and thus, the structural correctness of the resulting lithium poly-3, 6-dihydroxy-1, 2-benzenedicarboxylate borate is demonstrated.
Calculating dissociation energy: adopting a density functional method, and simulating a prepared poly-3, 6-dihydroxy-1, 2-phthalic acid lithium borate structure by Gaussian09 (Vision B.01) software, wherein MO is formed by a ligand and a boron atom2C3Six-membered ring, calculating lithium ion dissociation energy E from optimized configurationd(EdEqual to the anion energy plus the lithium ion energy minus the lithium salt energy), wherein B3LYP/6-31+ G (d) is adopted as the optimized configuration, B3LYP/6-311+ G (2df) is adopted as the energy of the optimized configuration, and the dissociation energy of the lithium poly-3, 6-dihydroxy-1, 2-phthalate borate is calculated to be 116 kcal/mol.
Example 4
This example provides a solid lithium poly (3, 6-dihydroxy-1, 2-benzenedicarboxylate) electrolyte
M is aluminum atom) according to the following steps:
to 200 g of dimethyl sulfoxide was added 19.80 g of 3, 6-dihydroxy-1, 2-benzenedicarboxylic acid
7.800 g of aluminum hydroxide and 4.196 g of lithium hydroxide monohydrate are stirred and reacted for 6 hours at 100 ℃ to obtain light yellow solution, and the light yellow solution is rotated and evaporated to obtain the poly-3, 6-dihydroxy-1, 2-phthalic acid lithium aluminate.
Structural characterization: the 13C nuclear magnetic resonance spectrum shows formants at chemical shifts of 115.2, 126.5, 151.3 and 179.7ppm, corresponding to carbon linked to carboxyl on the benzene ring, carbon linked to hydrogen on the benzene ring, carbon linked to a straight chain of hydroxyl on the benzene ring, and carboxyl carbon, respectively. The analysis result of the carbon, hydrogen and nitrogen elements is C: 42.05% and polymer formula (C)8O6The theoretical carbon content (42.11%) corresponding to AlLi) n is close, thus proving that the structure of the obtained lithium aluminate poly-3, 6-dihydroxy-1, 2-benzenedicarboxylate is correct.
Calculating dissociation energy: adopting a density functional method, and simulating and preparing the poly-lithium 3, 6-dihydroxy-1, 2-benzene dicarboxylic acid aluminate by Gaussian09 (Vision B.01) software, wherein MO is formed by a ligand and an aluminum atom2C3Six-membered ring, calculating lithium ion dissociation energy E from optimized configurationd(EdEqual to the anion energy plus the lithium ion energy minus the lithium salt energy), wherein B3LYP/6-31+ G (d) is adopted as the optimized configuration, B3LYP/6-311+ G (2df) is adopted as the energy of the optimized configuration, and the dissociation energy of the poly-3, 6-dihydroxy-1, 2-phthalic acid lithium aluminate is calculated to be 124 kcal/mol.
Example 5
This example provides a solid electrolyte of lithium poly (3, 5-dihydroxy-p-benzoquinone) -2, 6-disulfonate borate (II)
M is boron atom) according to the following steps:
33.20 g of 3, 5-dihydroxy-p-benzoquinone-2, 6-disulfonic acid are added to 200 g of methanol
6.183 g of boric acid and 4.196 g of lithium hydroxide monohydrate are stirred and reacted for 6 hours at room temperature to obtain a light yellow solution, and the light yellow solution is rotated and evaporated to obtain the lithium poly-3, 5-dihydroxy-p-benzoquinone-2, 6-disulfonate borate.
Structural characterization: the 13C nmr spectra showed formants at chemical shifts 123.2, 149.5 and 175.3ppm, corresponding to the carbon attached to the sulfonic acid group, the carbon attached to the hydroxyl group and the carbonyl carbon on the benzene ring, respectively. The analysis result of the carbon, hydrogen and nitrogen elements is C: 22.52% of the formula (C) with polymer6S2O10The theoretical carbon content (22.93%) corresponding to BLi) n was close, thus confirming that the structure of the obtained lithium poly-3, 5-dihydroxy-p-benzoquinone-2, 6-disulfonate borate was correct.
Calculating dissociation energy: adopting a density functional method, simulating and preparing a lithium poly-3, 5-dihydroxy-p-benzoquinone-2, 6-disulfonate borate structure by using Gaussian09(Revision B.01) software, wherein MO is formed by a ligand and a boron atom2SC2Six-membered ring calculated from the optimized configurationTo give lithium ion dissociation energy Ed(EdEqual to the energy of anions plus the energy of lithium ions minus the energy of lithium salts), wherein B3LYP/6-31+ G (d) is adopted for optimizing the configuration, B3LYP/6-311+ G (2df) is adopted for calculating the energy of the optimized configuration, and the dissociation energy of the lithium poly-3, 5-dihydroxy p-benzoquinone-2, 6-disulfonate borate is calculated to be 115 kcal/mol.
Comparative example 2: comparative example 2 use of the centrosymmetric ligand 2, 5-dihydroxy-p-benzoquinone-4, 6-disulfonic acid
Synthesizing a solid electrolyte of the lithium polyborate according to the following steps: 33.20 g of 2, 5-dihydroxy p-benzoquinone-4, 6-disulfonic acid, 6.183 g of boric acid and 4.196 g of lithium hydroxide monohydrate are added into 200 g of dimethyl sulfoxide, stirred and reacted for 6 hours at room temperature to obtain a light yellow solution, and the light yellow solution is subjected to rotary evaporation to obtain the lithium polyborate solid electrolyte.
Simulating the three-dimensional molecular configuration of the lithium poly-3, 5-dihydroxy-p-benzoquinone-2, 6-disulfonate borate prepared in example 5 and the lithium polyborate solid electrolyte prepared in comparative example 2 by using gaussian software, selecting B3LYP/6-31+ G (d) functional and group, using a molecular fragment containing 6 repeating units and taking a benzene ring as a terminal group as a structural model, simulating the accumulation of molecular chains in a three-dimensional space, wherein the molecular structural fragment and the three-dimensional configuration schematic diagram are shown in FIG. 2, white balls, gray balls, red balls, pink balls, yellow balls and purple balls in the figure represent hydrogen, carbon, oxygen, boron, sulfur and lithium ions respectively, a centrosymmetric ligand is used in comparative example 2 to form a linear polymer (shown as C in FIG. 2), while the structural fragment formed by a non-centrosymmetric ligand in example 6 is highly twisted and cannot be tightly accumulated in the three-dimensional space, thereby forming intrinsic micropores (as shown at D in fig. 2).
Example 6
This example provides a lithium poly (3, 5-dihydroxy-p-benzoquinone) -2, 6-disulfonate aluminate solid electrolyte
M is aluminum atom) according to the following steps:
at 200 g of N-methylpyrrolidine33.20 g of 3, 5-dihydroxy-p-benzoquinone-2, 6-disulfonic acid are added to the ketone
7.800 g of aluminum hydroxide and 4.196 g of lithium hydroxide monohydrate are stirred and reacted for 6 hours at the temperature of 100 ℃ to obtain light yellow solution, and the light yellow solution is rotated and evaporated to obtain the poly-3, 5-dihydroxy-p-benzoquinone-2, 6-disulfonic acid lithium aluminate.
Structural characterization:13c nuclear magnetic resonance spectrum shows formants at chemical shifts of 125.8, 151.1 and 174.3ppm, corresponding to the carbon attached to the sulfonic acid group, the carbon attached to the hydroxyl group and the carbonyl carbon on the benzene ring, respectively. The analysis result of the carbon, hydrogen and nitrogen elements is C: 21.61% of formula (C) with polymer6S2O10The theoretical carbon content (21.82%) corresponding to AlLi) n is close, thus proving that the structure of the obtained lithium aluminate poly-3, 5-dihydroxy-p-benzoquinone-2, 6-disulfonate is correct.
Calculating dissociation energy: adopting a density functional method, simulating a prepared 3, 5-dihydroxy p-benzoquinone-2, 6-disulfonic acid lithium aluminate structure by using Gaussian09(Revision B.01) software, wherein MO is formed by a ligand and an aluminum atom2SC2Six-membered ring, calculating lithium ion dissociation energy E from optimized configurationd(EdEqual to the energy of anions plus the energy of lithium ions minus the energy of lithium salts), wherein B3LYP/6-31+ G (d) is adopted for optimizing the configuration, B3LYP/6-311+ G (2df) is adopted for calculating the energy of the optimized configuration, and the dissociation energy of the poly-3, 5-dihydroxy p-benzoquinone-2, 6-disulfonic acid lithium aluminate is calculated to be 111 kcal/mol.
Example 7
This example provides a copolymer solid electrolyte, synthesized according to the following steps:
to 200 g of N-methylpyrrolidone was added 8.60 g of tetrahydroxybenzoquinone (A)
Symmetrical ligand), 9.90 g of 2, 3-dihydroxy-1, 4-benzenedicarboxylic acid
7.800 g of aluminum hydroxide and 4.196 g of lithium hydroxide monohydrateStirring and reacting for 6 hours under 100 ℃ to obtain a reddish brown solution, and performing rotary evaporation to obtain the lithium copolyoaluminate.
Structural characterization: the 13C nmr spectrum showed formants at chemical shifts 115.1, 118.2, 126.3, 143.7, 151.1, 175.8, 179.7 ppm. The analysis result of the carbon, hydrogen and nitrogen elements is C: 36.01% of a polymer of the formula (C)7O6The theoretical carbon content (36.27%) for AlLi) n is close, and therefore the resulting polymer is a copolymer, rather than a mixture of two polymers.
Comparative example 3: comparative example 3 use of a centrosymmetric ligand tetrahydroxybenzoquinone
Synthesizing a solid electrolyte of the lithium polyborate according to the following steps: adding 17.20 g of tetrahydroxybenzoquinone, 6.183 g of boric acid and 4.196 g of lithium hydroxide monohydrate into 200 g of water, stirring and reacting for 6 hours at room temperature to obtain a reddish brown solution, and performing rotary evaporation to obtain the lithium polyborate solid electrolyte.
Simulating three-dimensional molecular configurations of the copolymer solid electrolyte prepared in example 7 and the lithium polyborate solid electrolyte prepared in comparative example 3 by using gaussian software, selecting B3LYP/6-31+ G (d) functional and group, using a molecular fragment containing 6 repeating units and taking a benzene ring as a terminal group as a structural model, simulating the accumulation of a molecular chain in a three-dimensional space, wherein the schematic diagram of the molecular structure fragment and the three-dimensional configuration is shown in FIG. 3, white balls, gray balls, red balls, pink balls, yellow balls and purple balls in the figure represent hydrogen, carbon, oxygen, boron, sulfur and lithium ions respectively, the molecular structure of the lithium polyborate solid electrolyte of comparative example 3 is shown in A in FIG. 3, and a linear polymer (see B in FIG. 3) is formed by using a centrosymmetric ligand such as tetrahydroxybenzoquinone in comparative example 3, and is generally a dense and non-porous polymer; on the other hand, as shown in fig. 3C, when asymmetric monomers such as o-dihydroxy terephthalic acid and tetrahydroxybenzoquinone are copolymerized, the obtained polymer is a highly twisted molecular chain, and cannot be tightly packed in a three-dimensional space, so that intrinsic micropores are formed (see fig. 3D). The result shows that the asymmetric ligand and the symmetric ligand are copolymerized, the regular molecular configuration formed by the symmetric ligand can be inhibited, and the inherent microporous polymer solid electrolyte is formed.
Example 8
This example provides a solid electrolyte of lithium poly (4, 6-dihydroxy-1, 3-benzenedicarboxylate borate), (b
M is boron atom) according to the following steps:
to 200 g of dimethyl sulfoxide was added 19.80 g of 4, 6-dihydroxy-1, 3-benzenedicarboxylic acid
6.183 g of boric acid and 4.196 g of lithium hydroxide monohydrate are stirred and reacted for 6 hours at room temperature to obtain a pale yellow solution, and the pale yellow solution is subjected to rotary evaporation to obtain the lithium poly-4, 6-dihydroxy-1, 3-phthalate borate.
Structural characterization:13the C nuclear magnetic resonance spectrum has resonance peaks at chemical shifts of 103.1, 105.1, 136.1, 155.1 and 159.6ppm, and the analysis result of hydrocarbon nitrogen elements is C: 45.15% and polymer formula (C)8O6BLi) n corresponds to a close theoretical carbon content (45.28%) and thus, the structural correctness of the resulting lithium poly-4, 6-dihydroxy-1, 3-benzenedicarboxylate borate is demonstrated.
Calculating dissociation energy: adopting a density functional method, and simulating a prepared poly-4, 6-dihydroxy-1, 3-phthalic acid lithium borate structure by Gaussian09 (Vision B.01) software, wherein MO is formed by a ligand and a boron atom2C3Six-membered ring, calculating lithium ion dissociation energy E from optimized configurationd(EdEqual to the anion energy plus the lithium ion energy minus the lithium salt energy), the dissociation energy of the poly-4, 6-dihydroxy-1, 3-phthalic acid lithium borate is calculated by a density functional function method to be 130 kcal/mol.
Example 9
This example provides a lithium poly (4, 6-dihydroxy-1, 3-benzenedicarboxylate) solid electrolyte
M is an aluminum atom), anThe synthesis method comprises the following steps:
adding 19.80 g of 4, 6-dihydroxy-1, 3-phthalic acid, 7.800 g of aluminum hydroxide and 4.196 g of lithium hydroxide monohydrate into 200 g of dimethyl sulfoxide, stirring and reacting for 6 hours at 100 ℃ to obtain a light yellow solution, and performing rotary evaporation to obtain the lithium aluminate poly-4, 6-dihydroxy-1, 3-phthalic acid.
Structural characterization:13the C nmr spectra showed peaks at chemical shifts 105.2, 113.1, 134.5, 161.4 and 174.3ppm, which are assigned as shown. The analysis result of the carbon, hydrogen and nitrogen elements is C: 42.05% and polymer formula (C)8O6The theoretical carbon content (42.11%) corresponding to AlLi) n was close, thus demonstrating that the structure of the resulting lithium poly-4, 6-dihydroxy-1, 3-benzenedicarboxylate aluminate was correct.
Calculating dissociation energy: the dissociation energy of the poly-4, 6-dihydroxy-1, 3-phthalic acid lithium aluminate calculated by a density functional method is 144 kcal/mol.
Claims (10)
1. The inherent microporous polyaluminium/borate solid electrolyte is characterized in that the inherent microporous polyaluminium/borate solid electrolyte is an alkali metal salt of a coordination compound formed by at least one ligand Ar and a coordination atom M, wherein the structural formula of the ligand Ar is shown in the specification
At least one of the ligands Ar is a non-centrosymmetric structure,
the inherent micropore polyaluminium/borate solid electrolyte has a structural formula
Wherein M represents boron or aluminum, N represents an alkali metal element, N represents a degree of polymerization, and X represents1、X2Each independently selected from SO2CO or absent, Y is selected from
And Y is selected from-OH, -COOH, -SO3At least 2 substituents of H.
2. The intrinsically microporous polyaluminum/borate solid state electrolyte of claim 1, wherein the ligand Ar is selected from the group consisting of
3. The intrinsically microporous polyaluminium/borate solid state electrolyte of claim 1, wherein the ligand Ar and the coordinating atom M are capable of forming a five-, six-or seven-membered ring.
4. The intrinsically microporous polyaluminum/borate solid-state electrolyte of claim 3, wherein the ligand Ar forms MO with the coordinating atom M2C2Five-membered ring, MO2C3Six-membered ring, MO2SC2Six-membered rings or MO2C4A seven-membered ring.
5. The inherently microporous polyaluminum/borate solid-state electrolyte of claim 4, wherein said inherently microporous polyaluminum/borate solid-state electrolyte is selected from the group consisting of
6. The intrinsically microporous polyaluminium/borate solid state electrolyte of claim 1, wherein the alkali metal element is any one of lithium, sodium, and potassium.
7. A method of making the inherently microporous polyaluminium/borate solid state electrolyte of any of claims 1 to 6 comprising the steps of:
and adding the ligand Ar, boric acid or aluminum hydroxide and alkali into a polar solvent, stirring for reaction, and evaporating to obtain the inherent microporous polyaluminium/borate solid electrolyte.
8. The method of making an inherently microporous polyaluminium/borate solid state electrolyte of claim 7 wherein the polar solvent comprises water or a polar organic solvent.
9. The method of claim 8, wherein the polar organic solvent is selected from any one of methanol, ethanol, N-methylpyrrolidone, dimethylsulfoxide, and N, N-dimethylformamide.
10. A battery comprising the inherently microporous polyaluminium/borate solid state electrolyte of any of claims 1 to 6.
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