CN114069044B - Positive electrode material and lithium ion battery containing same - Google Patents
Positive electrode material and lithium ion battery containing same Download PDFInfo
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- CN114069044B CN114069044B CN202111257939.2A CN202111257939A CN114069044B CN 114069044 B CN114069044 B CN 114069044B CN 202111257939 A CN202111257939 A CN 202111257939A CN 114069044 B CN114069044 B CN 114069044B
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- 239000007774 positive electrode material Substances 0.000 title claims abstract description 79
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 33
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 7
- 239000013384 organic framework Substances 0.000 claims abstract description 7
- 150000002500 ions Chemical class 0.000 claims description 12
- 239000012634 fragment Substances 0.000 claims description 8
- 229910000510 noble metal Inorganic materials 0.000 claims description 6
- 239000011149 active material Substances 0.000 claims description 5
- 229910052737 gold Inorganic materials 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical group OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims 1
- 229920002554 vinyl polymer Polymers 0.000 claims 1
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 abstract description 15
- 239000003792 electrolyte Substances 0.000 abstract description 14
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 abstract description 9
- -1 iodide ions Chemical class 0.000 abstract description 6
- 230000000737 periodic effect Effects 0.000 abstract description 4
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 abstract description 4
- 230000033116 oxidation-reduction process Effects 0.000 abstract description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 45
- 239000000047 product Substances 0.000 description 15
- 239000000203 mixture Substances 0.000 description 14
- 238000002360 preparation method Methods 0.000 description 13
- 239000000243 solution Substances 0.000 description 13
- 239000002904 solvent Substances 0.000 description 13
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 12
- 150000001875 compounds Chemical class 0.000 description 10
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 10
- 238000001035 drying Methods 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- 101100207325 Arabidopsis thaliana TPPE gene Proteins 0.000 description 8
- 239000006258 conductive agent Substances 0.000 description 7
- 239000011259 mixed solution Substances 0.000 description 7
- 239000012046 mixed solvent Substances 0.000 description 6
- 239000002244 precipitate Substances 0.000 description 6
- 229910013872 LiPF Inorganic materials 0.000 description 5
- 101150058243 Lipf gene Proteins 0.000 description 5
- 239000000853 adhesive Substances 0.000 description 5
- 230000001070 adhesive effect Effects 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 5
- 229910000160 potassium phosphate Inorganic materials 0.000 description 5
- 235000011009 potassium phosphates Nutrition 0.000 description 5
- WLPUWLXVBWGYMZ-UHFFFAOYSA-N tricyclohexylphosphine Chemical compound C1CCCCC1P(C1CCCCC1)C1CCCCC1 WLPUWLXVBWGYMZ-UHFFFAOYSA-N 0.000 description 5
- 239000006245 Carbon black Super-P Substances 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- 239000002033 PVDF binder Substances 0.000 description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 239000007772 electrode material Substances 0.000 description 4
- 238000000227 grinding Methods 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 229920000098 polyolefin Polymers 0.000 description 4
- QLULGIRFKAWHOJ-UHFFFAOYSA-N pyridin-4-ylboronic acid Chemical compound OB(O)C1=CC=NC=C1 QLULGIRFKAWHOJ-UHFFFAOYSA-N 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- MWVTWFVJZLCBMC-UHFFFAOYSA-N 4,4'-bipyridine Chemical compound C1=NC=CC(C=2C=CN=CC=2)=C1 MWVTWFVJZLCBMC-UHFFFAOYSA-N 0.000 description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 3
- 239000010405 anode material Substances 0.000 description 3
- 239000012300 argon atmosphere Substances 0.000 description 3
- 150000001728 carbonyl compounds Chemical class 0.000 description 3
- 238000007872 degassing Methods 0.000 description 3
- 229910052740 iodine Inorganic materials 0.000 description 3
- 239000011630 iodine Substances 0.000 description 3
- 239000007773 negative electrode material Substances 0.000 description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- WGGLDBIZIQMEGH-UHFFFAOYSA-N 1-bromo-4-ethenylbenzene Chemical group BrC1=CC=C(C=C)C=C1 WGGLDBIZIQMEGH-UHFFFAOYSA-N 0.000 description 2
- 230000006978 adaptation Effects 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 150000002484 inorganic compounds Chemical class 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- IWDFHWZHHOSSGR-UHFFFAOYSA-N 1-ethylimidazole Chemical compound CCN1C=CN=C1 IWDFHWZHHOSSGR-UHFFFAOYSA-N 0.000 description 1
- IYVYLVCVXXCYRI-UHFFFAOYSA-N 1-propylimidazole Chemical compound CCCN1C=CN=C1 IYVYLVCVXXCYRI-UHFFFAOYSA-N 0.000 description 1
- HIDCNJIBRZBEPN-UHFFFAOYSA-N 2,4,5-triiodo-1h-imidazole Chemical compound IC1=NC(I)=C(I)N1 HIDCNJIBRZBEPN-UHFFFAOYSA-N 0.000 description 1
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 239000002482 conductive additive Substances 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 239000013310 covalent-organic framework Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 125000005647 linker group Chemical group 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 150000002898 organic sulfur compounds Chemical class 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
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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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
-
- 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
- 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
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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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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a positive electrode material and a lithium ion battery containing the positive electrode material, wherein the positive electrode material is based on three-center four-electron [ N … A ] n+ …N]Bridged two-dimensional halo-bonded organic framework molecules, wherein the A + Selected from I + Or an n-valent metal ion; the positive electrode material has a porous structure. The positive electrode material has a large number of redox sites due to the existence of iodide ions or n-valence metal ions and pyridine (or imidazole and the like) groups, so that the positive electrode material has higher specific capacity; meanwhile, the lithium ion battery has a porous structure, so that a large amount of electrolyte can be quickly absorbed to quickly transmit lithium ions; the positive electrode material also has an excellent and stable two-dimensional periodic structure, so that the cycle performance of the battery is improved. The positive electrode material has high oxidation-reduction potential, and can provide a high discharge voltage platform, so that the energy density of the battery is improved.
Description
Technical Field
The invention belongs to the technical field of electrode materials of lithium ion batteries and preparation thereof, and particularly relates to a positive electrode material and a lithium ion battery containing the positive electrode material, in particular to a covalent organic framework positive electrode material, a preparation method thereof and a battery containing the positive electrode material.
Background
The 21 st century energy crisis is attracting more and more attention, and the problems of energy shortage and environmental pollution have forced researchers to find other alternative energy sources, such as solar energy, wind energy, geothermal energy, biological energy, and battery-like storage devices, to be the focus of attention. The battery storage device has the dual roles of energy storage and release, so that the development of a novel lithium ion battery anode material with low cost, high efficiency and stable cycle performance is of great significance in preparing the battery device with high energy density.
However, the market places higher demands on the storage density and flexibility of lithium ion batteries, and thus, development of new electrode materials is required to meet the above demands. The conventional positive electrode material of the lithium ion battery is mainly an inorganic compound, and the development of the lithium ion battery using the inorganic compound as the positive electrode material is limited due to the problem of mining reserves. The organic positive electrode material can avoid the problem of the reserve of the lithium ion battery, has green sustainability and is an ideal positive electrode material of the lithium ion battery in the future. The electroactive organic positive materials at this stage can be broadly divided into the following categories: conductive polymers, organic sulfur compounds, organic radical compounds, and organic carbonyl compounds. Among them, organic carbonyl compounds have received great attention because of their high theoretical specific capacity. However, organic carbonyl compounds have problems of poor conductivity and poor cycle stability. Therefore, development of a novel organic positive electrode material is needed to have the advantages of large capacity and high cycle stability.
Disclosure of Invention
In order to solve the technical problems, the invention provides a positive electrode material, a preparation method and application thereof, wherein the positive electrode material is based on three-center four-electron [ N … A ] n+ …N]Bridged two-dimensional a-bond organic framework molecules and have a porous structure; the positive electrode material of the invention is characterized in that A n+ The existence of ions and pyridine (or imidazole and the like) groups has a large number of redox sites, so that the specific capacity is higher; meanwhile, the lithium ion battery has a porous structure, so that a large amount of electrolyte can be quickly absorbed to quickly transmit lithium ions; the positive electrode material also has an excellent and stable two-dimensional periodic structure, so that the cycle performance of the battery is improved. Therefore, the technical problems of poor conductivity and poor circulation stability of the organic lithium ion battery when the carbonyl material is used as the positive electrode material are solved.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
the invention provides a positive electrode material based on three-center four-electron [ N … A ] n+ …N]A bridged two-dimensional a-bond organic framework molecule, wherein the a n+ Selected from I + Or an n-valent metal ion; the positive electrode material has a porous structure.
According to the invention, the n-valent metal ion is, for example, a noble metal ion, which may be, in particular, au + 、 Ru 3+ 、Pt 2+ Or other noble metal ions.
According to the invention, the positive electrode material comprises one of the following structural fragments represented by the formulas I to IX:
in the formulas I to IX, A n+ X is as defined above 1 Selected from the group consisting of absent or divalent radicals, X 2 Selected from trivalent radicals, X 3 Selected from tetravalent groups.
According to the invention, when X 1 The positive electrode material comprises one of the following structural fragments shown in formula Ia, formula IIa or formula IIIa when the positive electrode material is not present:
in formula Ia, formula IIa and formula IIIa, A n+ Is as defined above.
According to the invention, X 1 Selected from divalent groups such as polyethylene terephthalate groups, polybutylene terephthalate groups.
According to the invention, a trivalent radical X 2 For example phenyl, the 1,3,5 positions of which are the attachment sites.
According to the invention, tetravalent radical X 3 For example vinyl groups, the 1,2 positions of which are the attachment sites.
According to the present invention, the positive electrode material including the structural fragment represented by formula VIII specifically includes the structural fragment represented by formula VIIIa as follows:
in formula VIIIa, the central ion I + Can also be replaced by Au + 、Ru 3+ 、Pt 2+ And other noble metal ions. In the invention, the structural stability of the material can be improved by introducing metal ions.
The invention also provides a positive plate which comprises the positive electrode material.
The invention also provides a lithium ion battery, which comprises the positive electrode material; alternatively, the positive electrode sheet is included.
The invention has the beneficial effects that:
the invention provides a three-center four-electron-based [ N … A n+ …N]A bridged two-dimensional a-bond organic framework molecule, and a positive electrode material having a porous structure; the positive electrode material of the invention is characterized in that A n+ The existence of ions and pyridine (or imidazole and the like) groups has a large number of redox sites, so that the specific capacity is higher; meanwhile, the lithium ion battery has a porous structure, so that a large amount of electrolyte can be quickly absorbed to quickly transmit lithium ions; the positive electrode material of the invention also has excellent and stable performanceThe two-dimensional periodic structure further improves the cycle performance of the battery. Therefore, the technical problems of poor conductivity and poor circulation stability of the organic lithium ion battery when the carbonyl material is used as the positive electrode material are solved. The positive electrode material has high oxidation-reduction potential, and can provide a high discharge voltage platform, so that the energy density of the battery is improved. The concrete steps are as follows:
(1) The anode material is a high molecular polymer, has a porous structure, can quickly absorb a large amount of electrolyte (the absorption time of the electrolyte on the anode material is 40-70% shorter than that of the conventional electrode material under the same electrode pole piece preparation process), and is insoluble in the current commercialized electrolyte, so that the electrode active material is effectively prevented from shuttling at two poles, and the cycle stability of a battery is improved.
(2) The positive electrode material of the present invention has a large number of redox sites due to the presence of iodide ions and pyridine (or imidazole, etc.) groups, and thus can provide specific capacity of a battery.
(3) The positive electrode material of the present invention also has an excellent, stable two-dimensional periodic structure in which iodine positive ions (I + ) Used as a linking moiety, tends to form stable, linear halogen bond interactions, thereby enhancing the cycling performance of the battery.
(4) I in the cathode material of the present invention + Can be Au-coated + Etc. to improve the cycling stability of the electrode.
(5) The positive electrode material of the invention can also be applied to solid-state batteries, quasi-solid-state batteries, and other positive electrode materials for ion batteries (for example, adding Mg (TFSI) by adjusting additives in the preparation process 2 To be suitable for use in magnesium ion batteries or to add naffsi to be suitable for use in sodium ion batteries).
Drawings
Fig. 1 is a cycle performance chart of lithium ion batteries manufactured in examples 1-2 and comparative examples 1-2.
Detailed Description
The invention also provides a preparation method of the positive electrode material, which comprises the following steps: in a compound containing an =n-groupThe object is a model unit and contains Ag + Is coordinated to form [ N … Ag ] + …N]Bridged organic framework molecules, and thus using A n+ In situ substitution [ N … Ag ] + …N]Ag in bridge + Ion formation to [ N … A n+ …N]Bridged organic framework molecules, i.e. the positive electrode material; a is that n+ Is as defined above.
According to the invention, the compound containing an =n-group is selected from one of the compounds represented by the following structural formulae: 4,4 '-bipyridine, 2' -bipyridine, imidazole (such as N-ethylimidazole, N-propylimidazole, 2,4, 5-triiodoimidazole, etc.) which is unsubstituted or optionally substituted by one or more alkyl groups, halogen, TPPE, etc., said TPPE having the following structural formula:
according to the invention, the compound containing an =n-group is mixed with Ag + Compound (A) n+ The dosage ratio of (2) is 1:1-1:5, and the ratio is 1:1, 1:2, 1:3, 1:4 and 1:5.
According to the invention, the Ag-containing material + The compound of (2) may be AgPF, for example 6 、AgSbF 6 、AgAsF 6 At least one of the following.
According to the invention, the A n+ Can be A-containing n+ At least one of the elements or compounds of (a) is provided.
According to the invention, the compound containing an =n-group is mixed with Ag + The compounds of (a) are added into the reaction system in the form of solution. For example, CHCl of the compound containing the=n-group is prepared separately 3 Mixed solution of MeOH and Ag-containing solution + The two solutions are mixed to obtain a reaction mixture. Preferably, CHCl 3 In a mixed solvent of MeOH and CHCl 3 The mixing volume ratio of MeOH is (50-150): (0-1), exemplary 50:0, 80:1, 100:1, 150:1.
According to the invention, the A n+ Is added into the reaction system in the form of solution. For example, A is prepared first n+ Is then mixed with the methanol solution of (C)Will contain A n+ Is added into the reaction system. Preferably, the said A-containing n+ The concentration of the methanol solution is 0.01 to 0.05mol/L, and exemplary is 0.01mol/L, 0.03mol/L, 0.05mol/L.
According to the invention, the A n+ In situ substitution [ N … Ag ] + …N]Ag in bridge + The reaction temperature of the ions is 140 to 180 ℃, and is exemplified by 140 ℃, 160 ℃ and 180 ℃. Further, the reaction time is 4 to 8 hours, and is exemplified by 4 hours, 6 hours, and 8 hours.
According to the invention, the preparation method of the positive electrode material further comprises the steps of decompressing the reaction mixture to remove the solvent, and drying the precipitate overnight to obtain the positive electrode material.
According to an exemplary embodiment of the invention, the A n+ Is I + . For example, the I + Provided by elemental iodine.
According to an exemplary embodiment of the present invention, the TPPE is prepared by reacting a feedstock comprising 1, 2-tetrakis (4-bromophenyl) ethylene and 4-pyridineboronic acid in the presence of palladium acetate, potassium phosphate, tricyclohexylphosphine.
Preferably, the using percentages of the raw materials of the 1, 2-tetra (4-bromophenyl) ethylene and 4-pyridine boric acid, the palladium acetate, the potassium phosphate and the tricyclohexylphosphine are 15-30%: 20-35%: 0.5 to 5 percent: 40-60%: 2-10%.
Preferably, the preparation of the TPPE is carried out in a solvent system. For example, the solvents are DMF and H 2 Mixed solvent of O. Further, in the mixed solvent, DMF and H 2 The mixing volume ratio of O is (5-15): 1, and exemplary are 5:1, 8:1, 10:1, and 15:1.
Preferably, the temperature of the reaction during the preparation of the TPPE is 120-160 ℃, and is exemplified by 120 ℃, 145 ℃ and 160 ℃. Further, the reaction time is 48 hours or more.
Preferably, the preparation of the TPPE further comprises concentrating the above mixture under reduced pressure, and grinding the resulting slurry. For example, the milling media is methylene chloride.
Preferably, the preparation of the TPPE alsoComprises washing and drying the ground product. For example, use H 2 The product was washed with O and dried over anhydrous sodium sulfate to purify the residue.
According to an exemplary embodiment of the present invention, the method for preparing the positive electrode material includes the steps of:
s1: adding 1, 2-tetra (4-bromophenyl) ethylene and 4-pyridineboronic acid, palladium acetate, potassium phosphate, tricyclohexylphosphine into DMF and H under argon atmosphere 2 O in a mixed solvent;
s2: heating and stirring the mixed solution for more than 48 hours;
s3: concentrating the mixture under reduced pressure, adding the obtained slurry into dichloromethane, and grinding;
s4: using H 2 Washing the product with O, drying with anhydrous sodium sulfate, and purifying the residue;
s5: adding the product into CHCl 3 In a mixed solution of MeOH, agBF 4 Adding the mixture into methanol, respectively and uniformly stirring, mixing, and stirring for more than 1 h;
s6: dropwise adding a methanol solution of iodine, and stirring for 6 hours after degassing treatment;
s7: the solvent was removed under reduced pressure and the precipitate was dried in vacuo overnight to give product XOF.
The invention also provides application of the positive electrode material as a positive electrode active material of a lithium ion battery.
The invention also provides a positive plate which comprises the positive electrode material.
According to the invention, the positive electrode sheet comprises a current collector and an active material layer positioned on at least one side surface of the current collector, wherein the active material layer comprises the positive electrode material.
According to the invention, the active material layer further comprises a conductive agent and a binder. Preferably, the mass ratio of the positive electrode material, the conductive additive and the binder is (6-8): (1-13): 1, exemplary 6:1: 1. 7:13: 1. 8:7: 1. 8:1: 1. 8:13:1.
the invention also provides a preparation method of the positive plate, which comprises the steps of uniformly dispersing the positive electrode material, the conductive agent and the adhesive in a solvent, coating the positive electrode material, the conductive agent and the adhesive on a current collector, and then vacuum drying the current collector to prepare the positive electrode film.
The invention also provides a lithium ion battery, which comprises the positive electrode material; alternatively, the positive electrode sheet is included.
According to the invention, the lithium ion battery further comprises a negative plate.
According to the invention, the lithium ion battery further comprises a separator.
According to the invention, the lithium ion battery further comprises an electrolyte. The type of electrolyte is not particularly limited in the present invention, and for example, a conventional commercial LiPF in the art can be used 6 A series of electrolytes.
The invention also provides a preparation method of the lithium ion battery, which comprises the following steps: the positive plate and the negative plate are separated by a diaphragm, electrolyte is injected, and the lithium ion battery is obtained through assembly.
For a further understanding of the present invention, preferred embodiments of the invention are described below in conjunction with the examples, but it is to be understood that these descriptions are merely intended to illustrate further the features and advantages of the invention and are not limiting of the invention.
The invention is further illustrated by the following examples.
Example 1
Preparing a positive electrode material:
under an argon atmosphere, 648mg of 1, 2-tetrakis (4-bromophenyl) ethylene and 737mg of 4-pyridineboronic acid, 67mg of palladium acetate, 1.4g of potassium phosphate, 140mg of tricyclohexylphosphine were added to 20ml of DMF and 2ml of H 2 O in a mixed solvent;
s2: heating and stirring the mixed solution at 145 ℃ for more than 48 hours;
s3: concentrating the reaction mixture obtained in the step S2 under reduced pressure, adding the obtained slurry into 100ml of dichloromethane, and grinding;
s4: using H 2 Washing the product, drying the product by anhydrous sodium sulfate, and purifying the residue;
s5: the product TPPE (32 mg) was added to CHCl 3 /MeOH(4ml,v:v=1: 3) 19mg of AgBF was mixed with the mixed solution of (C) 4 Adding into 3ml of methanol, respectively stirring uniformly, mixing, and stirring for more than 1 h;
s6: 3ml of a methanol solution of iodine (25 mg) was added dropwise thereto, and the mixture was subjected to degassing treatment and then stirred at 160℃for 6 hours;
s7: the solvent was removed under reduced pressure, and the precipitate was dried in vacuo overnight to give a product XOF-TPPE as a positive electrode material having the structural formula shown below:
preparing a positive electrode plate and a battery:
uniformly dispersing the positive electrode material (450 mg), conductive carbon black (Super-P) conductive agent (50 mg) and PVDF adhesive (50 mg) in a solvent, coating the mixture on a current collector, and then drying the mixture in vacuum to prepare a positive electrode film; the positive electrode film and the negative electrode material (metallic lithium) are separated by a separator (polyolefin porous film), and an electrolyte (1M LiPF is injected 6 /(ec+dec, 1:1)), and assembling to obtain the lithium ion battery.
The testing method comprises the following steps:
battery cycle number test: after the battery is assembled, a LAND blue battery test system is used for testing the cycle performance under the condition of 0.2C/0.2C charge-discharge current and 3.0V-4.4V charge-discharge voltage.
Comparative example 1
Preparing a positive electrode material:
under an argon atmosphere, 648mg of 1, 2-tetrakis (4-bromophenyl) ethylene and 737mg of 4-pyridineboronic acid, 67mg of palladium acetate, 1.4g of potassium phosphate, 140mg of tricyclohexylphosphine were added to 20ml of DMF and 2ml of H 2 O in a mixed solvent;
s2: heating and stirring the mixed solution at 145 ℃ for more than 48 hours;
s3: concentrating the mixture under reduced pressure, adding the obtained slurry into 100ml of dichloromethane, and grinding;
s4: using H 2 Washing the product, drying the product by anhydrous sodium sulfate, and purifying the residue;
s5: the above products are producedTPPE (32 mg) was added to CHCl 3 In a mixed solution of/MeOH (4 ml, v: v=1:3), 19mg of AgBF was added 4 Adding into 3ml of methanol;
s6: stirring for 6h at 160 ℃ after degassing treatment;
s7: the solvent was removed under reduced pressure, and the precipitate was dried in vacuo overnight to give a product MOF-TPPE having a structural formula as a positive electrode material represented by the following formula:
preparing a positive electrode plate and a battery:
uniformly dispersing the positive electrode material (450 mg), conductive carbon black (Super-P) conductive agent (50 mg) and PVDF binder (50 mg) in a solvent, coating the mixture on a current collector, and then drying the mixture in vacuum to prepare a positive electrode film; the positive electrode film and the negative electrode sheet (metallic lithium) are separated by a separator (polyolefin porous film), and an electrolyte (1M LiPF) is injected 6 /(ec+dec, 1:1)), and assembling to obtain the lithium ion battery.
Example 2
S1: agBF 4 (19 mg)/methanol (3 ml) was added dropwise 4,4' -bipyridine (15.6 g)/CHCl 3 (12 ml) in solution;
s2: the solution was stirred at room temperature for 1 hour and I was added 2 (25mg)/CHCl 3 (3 ml) of a solution;
s3: the mixture was stirred for an additional 1 hour and the solvent was removed under reduced pressure (without heating);
s4: the precipitate was dried under vacuum overnight to give the product XOF-BPy as a positive electrode material of the formula:
preparing a positive electrode plate and a battery:
uniformly dispersing the positive electrode material (450 mg), conductive carbon black (Super-P) conductive agent (50 mg) and PVDF adhesive (50 mg) in a solvent, coating the mixture on a current collector, and then drying the mixture in vacuum to prepare a positive electrode film; will be spentThe positive electrode film and the negative electrode material (metallic lithium) are separated by a separator (polyolefin porous film), and an electrolyte (1M LiPF) is injected 6 /(ec+dec, 1:1)), and assembling to obtain the lithium ion battery.
Comparative example 2
S1: agBF 4 (19 mg)/methanol (3 ml) was added dropwise 4, 4-bipyridine (15.6 g)/CHCl 3 (12 ml) in solution;
s2: the solution was stirred at room temperature for 1 hour;
s3: removing the solvent under reduced pressure without heating;
s4: the precipitate was dried under vacuum overnight to give product XOF-Bpy, a positive electrode material having the structural formula shown below:
preparing a positive electrode plate and a battery:
uniformly dispersing the positive electrode material (450 mg), conductive carbon black (Super-P) conductive agent (50 mg) and PVDF adhesive (50 mg) in a solvent, coating the mixture on a current collector, and then drying the mixture in vacuum to prepare a positive electrode film; the positive electrode film and the negative electrode material (metallic lithium) are separated by a separator (polyolefin porous film), and an electrolyte (1M LiPF is injected 6 /(ec+dec, 1:1)), and assembling to obtain the lithium ion battery. Fig. 1 is a graph showing cycle performance of the batteries manufactured in examples 1-2 and comparative examples 1-2. As can be seen from the figures: table 1 list of performance test data for batteries
As can be seen from the battery cycle performance diagram of FIG. 1, the cycle performance of the positive electrode material prepared by the invention is obviously improved (up to 51.8 percent) compared with that of the conventional positive electrode material, so that the positive electrode material can obviously improve the battery cycle performance.
While the foregoing is directed to the preferred embodiments of the present invention, it will be appreciated by those skilled in the art that various modifications and adaptations can be made without departing from the principles of the present invention, and such modifications and adaptations are intended to be comprehended within the scope of the present invention.
Claims (7)
1. A positive electrode material is characterized by being based on three-center four-electron [ N … A ] n+ …N]A bridged two-dimensional a-bond organic framework molecule, the positive electrode material having one of the structural fragments represented by the following formulas I, II, IV to IX:
the positive electrode material including the structural fragment represented by formula VIII specifically includes the structural fragment represented by formula VIIIa below:
wherein in the formulas I, II, IV and IX, X 1 Selected from the group consisting of absent or divalent groups, said divalent groups being poly (terephthalate) groups; x is X 2 Selected from trivalent radicals, X 3 Selected from tetravalent groups; the A is n+ Selected from I + Or n-valent metal ion of Au + 、Ru 3+ 、Pt 2+ And other noble metal ionsOne less;
in formula VIIIa, I + Also replaced by Au + 、Ru 3+ 、Pt 2+ Other noble metal ions;
the positive electrode material has a porous structure.
2. The positive electrode material according to claim 1, wherein X 1 Is selected from the non-existent positive electrode material, and the positive electrode material comprises one of the following structural fragments shown in the formulas Ia and IIa:
in formula Ia, formula IIa, A n+ Selected from I + Or n-valent metal ion of Au + 、Ru 3+ 、Pt 2+ And at least one of other noble metal ions.
3. The positive electrode material according to claim 1, wherein the trivalent group X 2 Is phenyl, and the 1,3 and 5 positions are connecting sites.
4. The positive electrode material according to claim 1, wherein the tetravalent group X 3 Is vinyl, and the 1,2 and 2 positions are connecting sites.
5. A positive electrode sheet, characterized in that the positive electrode sheet comprises the positive electrode material according to any one of claims 1 to 4.
6. The positive electrode sheet according to claim 5, wherein the positive electrode sheet comprises a current collector and an active material layer on at least one side surface of the current collector, and the active material layer comprises the positive electrode material.
7. A lithium ion battery comprising the positive electrode material of any one of claims 1-4; alternatively, a positive electrode sheet comprising any one of claims 5 to 6.
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