CN116751459A - Preparation method and application of LNO-MOF nanocomposite - Google Patents
Preparation method and application of LNO-MOF nanocomposite Download PDFInfo
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- 239000002114 nanocomposite Substances 0.000 title claims abstract description 72
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 57
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000003792 electrolyte Substances 0.000 claims abstract description 36
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 36
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000002105 nanoparticle Substances 0.000 claims abstract description 27
- 229910013553 LiNO Inorganic materials 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 15
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000000843 powder Substances 0.000 claims abstract description 12
- 239000012046 mixed solvent Substances 0.000 claims abstract description 11
- 239000002904 solvent Substances 0.000 claims abstract description 11
- 238000010438 heat treatment Methods 0.000 claims abstract description 9
- 238000005406 washing Methods 0.000 claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 7
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims abstract description 6
- 235000019253 formic acid Nutrition 0.000 claims abstract description 6
- 238000001816 cooling Methods 0.000 claims abstract description 4
- 238000001914 filtration Methods 0.000 claims abstract description 4
- 238000003756 stirring Methods 0.000 claims abstract description 4
- 239000002253 acid Substances 0.000 claims abstract description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims abstract description 3
- 150000002148 esters Chemical class 0.000 claims abstract description 3
- GGROONUBGIWGGS-UHFFFAOYSA-N oxygen(2-);zirconium(4+);hydrate Chemical compound O.[O-2].[O-2].[Zr+4] GGROONUBGIWGGS-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000000203 mixture Substances 0.000 claims description 17
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 6
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 4
- -1 1,3, 5-benzene tricarboxylic acid ester Chemical class 0.000 claims description 3
- 102000020897 Formins Human genes 0.000 claims description 3
- 108091022623 Formins Proteins 0.000 claims description 3
- 230000000630 rising effect Effects 0.000 claims description 3
- QMKYBPDZANOJGF-UHFFFAOYSA-N trimesic acid Natural products OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 claims description 3
- 238000000643 oven drying Methods 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 229910052744 lithium Inorganic materials 0.000 abstract description 28
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 22
- 239000011148 porous material Substances 0.000 abstract description 7
- 229920000642 polymer Polymers 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 15
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 12
- 239000000463 material Substances 0.000 description 12
- 230000001351 cycling effect Effects 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 239000000243 solution Substances 0.000 description 9
- 229910013872 LiPF Inorganic materials 0.000 description 6
- 229910013870 LiPF 6 Inorganic materials 0.000 description 6
- 101150058243 Lipf gene Proteins 0.000 description 6
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 6
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 230000008021 deposition Effects 0.000 description 4
- 239000008151 electrolyte solution Substances 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 4
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- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000008439 repair process Effects 0.000 description 2
- 230000001502 supplementing effect Effects 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
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- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
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- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Classifications
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- 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
- H01M10/0566—Liquid materials
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/008—Supramolecular polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/28—Nitrogen-containing compounds
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- 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
- H01M10/0566—Liquid materials
- H01M10/0567—Liquid materials characterised by the additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
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- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
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- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Secondary Cells (AREA)
Abstract
The invention provides a preparation method and application of an LNO-MOF nanocomposite, wherein the method comprises the following steps: s1, dissolving zirconium trioxide and 1,3, 5-benzene trimethyl acid ester in a mixed solvent of N, N-dimethylformamide and formic acid, and heating in an oven to react; s2, cooling to room temperature after the reaction is finished, filtering and collecting MOF powder, and washing the MOF powder by adopting N, N-dimethylformamide; s3, immersing the washed MOF powder into methanol for solvent exchange, and drying in vacuum to obtain MOF nano particles; s4, immersing the MOF nano particles into LiNO 3 Stirring in methanol solution 24And h, washing by adopting methanol, and drying in an oven to obtain the LNO-MOF nanocomposite. According to the technical scheme, the preparation method is simple and reliable, and the prepared LNO-MOF nanocomposite is in the form of nano particles and LiNO 3 The polymer is easily distributed in the pore canal of the MOF nano particles, and can effectively improve the cycle stability of the lithium battery when being applied to the electrolyte of the lithium ion battery.
Description
Technical Field
The invention relates to the technical field of nanocomposite materials, in particular to a preparation method and application of an LNO-MOF nanocomposite material.
Background
With the high-speed development of new energy automobiles and wearable equipment, people put forward higher and urgent demands on the development of new energy. In recent years, lithium ion batteries have attracted great attention by virtue of their unique advantages of high energy density, low self-discharge rate, long cycle life, green environmental protection, and the like. However, the growth of lithium dendrites and low lithium cycling efficiency tend to lead to rapid failure of the battery with certain safety implications.
Lithium Metal Anodes (LMAs) are considered the optimal choice of high energy density energy storage device anode materials due to their ultra-high theoretical specific capacity (3860 mAh/g) and extremely low operating potential (-3.04 v vs. However, the unstable SEI film of lithium metal makes lithium deposition uneven, lithium dendrite is easy to form, short circuit failure of the battery is caused, potential safety hazard exists, and meanwhile, the complex interface reaction between lithium and electrolyte leads to continuous consumption of active lithium and electrolyte, so that the service life of the battery is greatly shortened. A prerequisite for high energy density lithium batteries is the successful adaptation to the limited Li of thin lithium metal anodes, which requires an efficient method to increase the coulombic efficiency of the lithium metal anode. Solid electrolyte interfacial films (SEIs) are clearly critical to improving coulombic efficiency. Mechanically and chemically stable SEI films with high ionic conductivity promote uniform ion flux and uniform Li deposition/dissolution, thereby minimizing dendrite formation and improving coulombic efficiency of lithium metal anode, improving cycle stability and ploidy of lithium battery.
Therefore, how to form a stable SEI film, ensure the progress of electrochemical reaction, and improve the high specific capacity and the cycling stability of the lithium battery becomes a technical problem to be solved urgently.
Disclosure of Invention
The present invention aims to solve at least one of the technical problems existing in the prior art or related art.
Therefore, an object of the present invention is to provide a preparation method of an LNO-MOF nanocomposite, an LNO-MOF nanocomposite and applications thereof, wherein the preparation method of the LNO-MOF nanocomposite is simple and reliable, the LNO-MOF nanocomposite is in a nano-scale particle shape, and LiNO 3 Is easily distributed in the pore canal of the MOF nano-particle, and 1mg of LiNO in the LNO-MOF nano-composite material 3 Can reach 0.23mg, and can effectively improve the cycle stability of the lithium battery when being applied to the electrolyte of the lithium ion battery.
In order to achieve the above object, a technical solution of a first aspect of the present invention provides a preparation method of an LNO-MOF nanocomposite, including the steps of:
s1, dissolving zirconium trioxide and 1,3, 5-benzene trimethyl acid ester in a mixed solvent of N, N-dimethylformamide and formic acid, and heating in an oven to react;
s2, cooling to room temperature after the reaction is finished, filtering and collecting MOF powder, and washing the MOF powder by adopting N, N-dimethylformamide;
s3, immersing the washed MOF powder into methanol for solvent exchange, and drying in vacuum to obtain MOF nano particles;
s4, immersing the MOF nano particles into LiNO 3 Stirring the mixture in a methanol solution for 24 hours, washing the mixture by using methanol, and drying the mixture in an oven to obtain the LNO-MOF nanocomposite.
In the technical scheme, the preparation method of the LNO-MOF nanocomposite is simple and reliable, the raw materials are low in price and suitable for mass production, and the prepared LNO-MOF nanocomposite is in the form of nano particles and has the characteristics of good film forming property and good cycle performance, and the LiNO 3 Is easily distributed in the pore canal of the MOF nano-particle, and 1mg of LiNO in the LNO-MOF nano-composite material 3 Can reach 0.23mg, and can well disperse LiNO when applied to lithium ion battery electrolyte 3 During battery operation, liNO 3 Is continuously consumed to repair the SEI layer, and the LNO-MOF nanocomposite can continuously supplement LiNO 3 Thereby improvingHigh specific capacity and cycle stability of the battery.
In the above technical solution, preferably, in step S1, specific conditions for heating in an oven to perform a reaction are: the temperature is 130 ℃, the reaction time is 48 hours, and the temperature rising rate is 2 ℃ for min -1 。
In the technical scheme, the stability of the prepared MOF nano particles is further ensured, so that the structural integrity of the LNO-MOF nano composite material can be ensured.
In any of the above technical solutions, preferably, the volume ratio of N, N-dimethylformamide to formic acid is 1:1; the dosage of the zirconium oxide is 1.60 mg-1.65 mg of zirconium oxide added into every 100mL of mixed solvent; 0.35 mg-0.40 mg of 1,3, 5-benzene tricarboxylic acid ester is added into each 100mL mixed solvent.
In the technical scheme, the stability and the balance of the prepared MOF nano-particles and the preparation method of the MOF nano-particles for LiNO are further ensured 3 Wherein, 0.97mg of zirconium oxide and 0.21mg of 1,3, 5-trimellitate are added into 60mL of mixed solvent, and the prepared LNO-MOF nanocomposite has better performance.
In any one of the above embodiments, preferably, in step S4, liNO 3 The concentration of the methanol solution was 2mol/L, and the solution was washed three times with methanol.
In this technical scheme, liNO 3 The concentration of the methanol solution is 2mol/L, thereby further ensuring LiNO 3 Is completely impregnated into the pore canal of the MOF nanoparticle. Washing with methanol for three times to remove residual LiNO outside MOF nanoparticles 3 And removing the catalyst, thereby guaranteeing the stability and film forming performance of the LNO-MOF nanocomposite obtained after vacuum drying.
In any of the above technical solutions, preferably, in step S4, specific conditions for oven drying are: the temperature is 100 ℃, the reaction time is 10 hours, and the heating rate is 1-5 ℃/min.
In the technical scheme, the methanol solvent can be removed, and meanwhile, the stability of the LNO-MOF nanocomposite is further ensured, and the stability of a lithium battery is better improved.
The technical scheme of the second aspect of the invention provides an LNO-MOF nanocomposite, which is prepared from the LNO-MOF nanocomposite in the technical scheme and takes the shape of nano particles.
In the technical scheme, the LNO-MOF nanocomposite is in a nano-scale particle shape, is convenient to be added into lithium ion battery electrolyte, and is LiNO 3 Is easily distributed in the pore canal of the MOF nano-particle, and 1mg of LiNO in the LNO-MOF nano-composite material 3 Can reach 0.23mg.
The technical scheme of the third aspect of the invention provides application of the LNO-MOF nanocomposite in lithium ion battery electrolyte.
The LNO-MOF nanocomposite is added into the lithium ion battery electrolyte, so that the stability of the lithium battery can be remarkably improved. After the LNO-MOF nano composite material is added, liNO can be well dispersed in the electrolyte 3 During battery operation, liNO 3 After being continuously consumed, the SEI film is repaired, and the LNO-MOF nanocomposite can continuously supplement LiNO 3 Thereby forming a stable SEI film, improving safety performance, and simultaneously supplementing active lithium into the electrolyte. After the LNO-MOF nanocomposite is added, the lithium battery still shows good cycling stability after 300 times of cycling, the capacity retention rate is more than 90%, and the specific capacity after 10 times of cycling is still maintained at about 760 mAh/g.
The preparation method of the LNO-MOF nanocomposite, the LNO-MOF nanocomposite and the application thereof provided by the invention have the following beneficial technical effects:
(1) The preparation method of the LNO-MOF nanocomposite provided by the invention is simple and reliable, the raw materials are low in cost, the LNO-MOF nanocomposite is suitable for large-scale production, and the prepared LNO-MOF nanocomposite is in the form of nano particles and has the characteristics of good film forming property and good cycle performance.
(2) LNO-MOF nanocomposite material prepared by the invention and LiNO 3 Is easily distributed in the pore canal of the MOF nano-particle, and 1mg of LiNO in the LNO-MOF nano-composite material 3 Can reach 0.23mg.
(3) LNO-MOF sodium prepared by the inventionWhen the rice composite material is applied to lithium ion battery electrolyte, liNO can be well dispersed in the electrolyte 3 During battery operation, liNO 3 After being continuously consumed, the SEI film is repaired, and the LNO-MOF nanocomposite can continuously supplement LiNO 3 Thereby forming a stable SEI film, improving safety performance, and simultaneously supplementing active lithium into the electrolyte. After the LNO-MOF nanocomposite is added, the lithium battery still shows good cycling stability after 300 times of cycling, the capacity retention rate is more than 90%, and the specific capacity after 10 times of cycling is still maintained at about 760 mAh/g.
(4) The LNO-MOF nanocomposite prepared by the method is applied to lithium ion battery electrolyte and is prepared from LiNO 3 The interface layer formed by decomposition is beneficial to improving electrochemical kinetics of lithium deposition/dissolution, and can obviously improve the cycle stability of the lithium ion battery.
(5) The LNO-MOF nanocomposite prepared by the method is applied to lithium ion battery electrolyte, is favorable for forming a stable SEI film, has lower battery resistance, is more stable, and further reduces electrolyte consumption and lithium pulverization in the circulating process.
Additional aspects and advantages of the invention will be set forth in part in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention.
Drawings
The foregoing and/or additional aspects and advantages of the invention will become apparent and may be better understood from the following description of embodiments taken in conjunction with the accompanying drawings in which:
FIG. 1 shows an electron microscope image of an LNO-MOF nanocomposite prepared by the preparation method of an LNO-MOF nanocomposite according to the present invention;
FIG. 2 shows a comparison graph of cyclic voltammograms of lithium ion battery electrolyte prepared in example 3 and lithium ion battery prepared in comparative example, respectively, according to the present invention;
fig. 3 is a graph showing comparison of resistance test results of the lithium ion battery electrolyte prepared in example 3 and the lithium ion battery prepared in comparative example, respectively, according to the present invention;
FIG. 4 is a graph showing the comparison of the cycle performance test curves of the lithium ion battery electrolyte prepared in example 3 and the lithium ion battery prepared in comparative example, respectively, according to the present invention;
fig. 5 shows a ratio performance comparison graph of the lithium ion battery electrolyte prepared in example 3 according to the present invention and the lithium ion battery prepared in comparative example, respectively.
Detailed Description
The invention discloses a preparation method of an LNO-MOF nanocomposite, the LNO-MOF nanocomposite and application thereof, and a person skilled in the art can refer to the content of the LNO-MOF nanocomposite and properly improve the technological parameters. It is expressly noted that all such similar substitutions and modifications will be apparent to those skilled in the art, and are deemed to be included in the present invention. While the methods and applications of this invention have been described in terms of preferred embodiments, it will be apparent to those skilled in the relevant art that variations and modifications can be made in the methods and applications described herein, and in the practice and application of the techniques of this invention, without departing from the spirit or scope of the invention.
The invention is further illustrated by the following examples:
a method for preparing an LNO-MOF nanocomposite, comprising the steps of:
s102, dissolving 0.97mg of zirconium oxide and 0.21mg of 1,3, 5-trimellitate in a mixed solvent consisting of 30mLN, N-dimethylformamide and 30mL of formic acid, placing the mixed solvent in an oven, heating the mixed solvent for reaction at 130 ℃ for 48h at a temperature rising rate of 2 ℃ for min -1 ；
S104, cooling to room temperature after the reaction is finished, filtering and collecting MOF powder, and washing the MOF powder with N, N-dimethylformamide for three times;
s106, immersing the washed MOF powder into methanol for solvent exchange, and drying in vacuum to obtain MOF nano particles;
s108, immersing the MOF nano particles into 2mol/L LiNO 3 Stirring in methanol solution for 24 hr, washing with methanol three times, and oven dryingDrying, specifically, reacting at 100 ℃ for 10 hours at a heating rate of 1-5 ℃/min to obtain the LNO-MOF nanocomposite.
The LNO-MOF nanocomposite material is in a nano-scale particle shape, and LiNO 3 Is easily distributed in the pore canal of the MOF nano-particle, and LiNO in the 1mgLNO-MOF nano-composite material 3 Can reach 0.23mg.
Example 1
Preparing lithium ion battery electrolyte: the solvent is a mixture of Ethylene Carbonate (EC), dimethyl carbonate (DMC) and ethylmethyl carbonate EMC, the volume ratio is 1:1:1, and LiPF is added 6 ，LiPF 6 In a glove box filled with nitrogen, 30mg of the prepared LNO-MOF nanocomposite was added to 100mL of the electrolyte solution, and the mixture was uniformly mixed.
Example 2
Preparing lithium ion battery electrolyte: the solvent is a mixture of Ethylene Carbonate (EC), dimethyl carbonate (DMC) and ethylmethyl carbonate EMC, the volume ratio is 1:1:1, and LiPF is added 6 ，LiPF 6 In a glove box filled with nitrogen, 40mg of the prepared LNO-MOF nanocomposite was added to 100mL of the electrolyte solution, and the mixture was uniformly mixed.
Example 3
Preparing lithium ion battery electrolyte: the solvent is a mixture of Ethylene Carbonate (EC), dimethyl carbonate (DMC) and ethylmethyl carbonate EMC, the volume ratio is 1:1:1, and LiPF is added 6 ，LiPF 6 In a glove box filled with nitrogen, 50mg of the prepared LNO-MOF nanocomposite was added to 100mL of the electrolyte solution, and the mixture was uniformly mixed.
Example 4
Preparing lithium ion battery electrolyte: the solvent is a mixture of Ethylene Carbonate (EC), dimethyl carbonate (DMC) and ethylmethyl carbonate EMC, the volume ratio is 1:1:1, and LiPF is added 6 ，LiPF 6 In a glove box filled with nitrogen, 60mg of the prepared LNO-MOF nanocomposite was added to 100mL of the electrolyte solution, and the mixture was uniformly mixed.
Example 5
Preparing lithium ion battery electrolyte: the solvent is a mixture of Ethylene Carbonate (EC), dimethyl carbonate (DMC) and ethylmethyl carbonate EMC, the volume ratio is 1:1:1, and LiPF is added 6 ，LiPF 6 70mg of the prepared LNO-MOF nanocomposite was added to 100mL of the electrolyte in a glove box filled with nitrogen, and the mixture was uniformly mixed.
Comparative example
Preparing lithium ion battery electrolyte: the solvent is a mixture of Ethylene Carbonate (EC), dimethyl carbonate (DMC) and ethylmethyl carbonate EMC, the volume ratio is 1:1:1, and LiPF is added 6 ，LiPF 6 The concentration of (C) was 1mol/L.
Assembling a battery: the lithium ion battery electrolytes of examples 1 to 5 and comparative example were used, respectively, and a lithium sheet was used as a negative electrode and an NCM material was used as a positive electrode to assemble a lithium ion battery.
The lithium ion batteries assembled by using the lithium ion battery electrolytes of examples 1 to 5 and comparative examples were subjected to resistance test and cycle performance test, respectively, and the test results are shown in table 1 below.
TABLE 1 results of testing LNO-MOF nanocomposite lithium ion batteries at different levels
Analysis of results
As can be seen from table 1, the effect of example 3 is better, and when 50mg of lno-MOF nanocomposite is added, not only the compatibility in the electrolyte is good, but also the stability of the lithium battery can be better improved.
The lithium ion batteries assembled using the lithium ion battery electrolytes of example 3 and comparative example were subjected to cyclic voltammetry test, resistance test, cyclic performance test, and rate performance test, respectively, and the results thereof are shown in fig. 2 to 5.
As shown in fig. 2, the polarization overpotential in example 3 is significantly lower than that in the comparative example, the electrochemical kinetics of lithium deposition/dissolution is significantly improved, and the cycle stability of the lithium ion battery is significantly improved.
As shown in fig. 3, the resistance of the comparative example is always higher, the decrease with time is not obvious, the resistance can still reach about 85 Ω after 600 hours of cycling, the resistance of the example 3 is obviously reduced compared with the comparative example, the SEI film is gradually stable and is rich in high ion conductive substances, the resistance is obviously reduced in the cycling process of the lithium ion battery containing the LNO-MOF electrolyte, and the resistance can be reduced to about 25 Ω after 600 hours of cycling.
As shown in fig. 4, the comparative example has poor cycle stability, the capacity retention rate is maintained at about 86% after 300 cycles, while the example 3 has good cycle stability, the capacity retention rate is still maintained at 91.97% after 300 cycles, and the addition of the LNO-MOF nanocomposite allows the lithium metal anode to form a more stable SEI film, reducing electrolyte consumption and Li pulverization during the cycle.
As shown in fig. 5, the specific capacity of the comparative example after the initial discharge at a rate of 1C/10C was about 755mAh/g, the specific capacity after 10 cycles was maintained at about 745mAh/g, and the specific capacity of the comparative example after 10 cycles was maintained at about 760mAh/g, while the specific capacity after 10 cycles was still maintained at about 772mAh/g at a rate of 1C/10C of example 3, which is far superior to the comparative example.
The LNO-MOF nanocomposite can be added to well disperse LiNO in electrolyte 3 ，LiNO 3 Can form stable SEI film on sodium metal cathode, and the SEI film with high ion conductivity can promote Li + The deposited Li is transported and adjusted to a particle structure, thereby improving Li cycle efficiency. During battery operation, liNO 3 Is continuously consumed to repair the SEI layer, and the LNO-MOF nanocomposite can continuously supplement LiNO 3 So that the cathode LMA can be relatively stable.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (8)
1. A method for preparing an LNO-MOF nanocomposite, comprising the steps of:
s1, dissolving zirconium trioxide and 1,3, 5-benzene trimethyl acid ester in a mixed solvent of N, N-dimethylformamide and formic acid, and heating in an oven to react;
s2, cooling to room temperature after the reaction is finished, filtering and collecting MOF powder, and washing the MOF powder by adopting N, N-dimethylformamide;
s3, immersing the washed MOF powder into methanol for solvent exchange, and drying in vacuum to obtain MOF nano particles;
s4, immersing the MOF nano particles into LiNO 3 Stirring the mixture in a methanol solution for 24 hours, washing the mixture by using methanol, and drying the mixture in an oven to obtain the LNO-MOF nanocomposite.
2. The method for preparing LNO-MOF nanocomposite as claimed in claim 1, wherein,
in the step S1, the specific conditions for heating in an oven to react are as follows: the temperature is 130 ℃, the reaction time is 48 hours, and the temperature rising rate is 2 ℃ for min -1 。
3. The method for preparing LNO-MOF nanocomposite as claimed in claim 1, wherein,
the volume ratio of the N, N-dimethylformamide to the formic acid is 1:1;
the dosage of the zirconium oxide is 1.60 mg-1.65 mg of zirconium oxide added into every 100mL of mixed solvent;
the dosage of the 1,3, 5-benzene tricarboxylic acid ester is 0.35 mg-0.40 mg of the 1,3, 5-benzene tricarboxylic acid ester in each 100mL mixed solvent.
4. A method for preparing an LNO-MOF nanocomposite as set forth in any one of claims 1 to 3, wherein,
in step S4, liNO 3 The concentration of the methanol solution was 2mol/L, and the solution was washed three times with methanol.
5. The method for preparing LNO-MOF nanocomposite as claimed in claim 4, wherein,
in step S4, specific conditions for oven drying are: the temperature is 100 ℃, the reaction time is 10 hours, and the heating rate is 1 ℃/min to 5 ℃/min.
6. An LNO-MOF nanocomposite, characterized in that it is prepared by the preparation method of the LNO-MOF nanocomposite according to any one of claims 1 to 5, and is in the form of nano-sized particles.
7. Use of the LNO-MOF nanocomposite of claim 6 in lithium ion battery electrolytes.
8. The use of LNO-MOF nanocomposite according to claim 7, wherein the LNO-MOF nanocomposite is used in an amount of 0.30-0.70mg/mL lithium ion battery electrolyte.
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