CN110256472A - Indium-aromatic carboxylic acids porous coordination and preparation method thereof and the application in lithium ion battery - Google Patents
Indium-aromatic carboxylic acids porous coordination and preparation method thereof and the application in lithium ion battery Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 11
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 11
- 239000003446 ligand Substances 0.000 claims abstract description 26
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims abstract description 13
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 12
- 150000001450 anions Chemical class 0.000 claims abstract description 11
- 150000002394 hexacarboxylic acid derivatives Chemical class 0.000 claims abstract description 10
- MNWFXJYAOYHMED-UHFFFAOYSA-N hexane carboxylic acid Natural products CCCCCCC(O)=O MNWFXJYAOYHMED-UHFFFAOYSA-N 0.000 claims abstract description 10
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 9
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims abstract description 7
- 230000005611 electricity Effects 0.000 claims description 30
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 28
- 229910052744 lithium Inorganic materials 0.000 claims description 28
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 9
- -1 aromatic carboxylic acids Chemical class 0.000 claims description 7
- SUAKHGWARZSWIH-UHFFFAOYSA-N N,N‐diethylformamide Chemical compound CCN(CC)C=O SUAKHGWARZSWIH-UHFFFAOYSA-N 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 4
- QNRATNLHPGXHMA-XZHTYLCXSA-N (r)-(6-ethoxyquinolin-4-yl)-[(2s,4s,5r)-5-ethyl-1-azabicyclo[2.2.2]octan-2-yl]methanol;hydrochloride Chemical compound Cl.C([C@H]([C@H](C1)CC)C2)CN1[C@@H]2[C@H](O)C1=CC=NC2=CC=C(OCC)C=C21 QNRATNLHPGXHMA-XZHTYLCXSA-N 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 229910052738 indium Inorganic materials 0.000 claims 3
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims 3
- 150000001408 amides Chemical class 0.000 claims 2
- 238000007599 discharging Methods 0.000 abstract description 14
- 238000000034 method Methods 0.000 abstract description 6
- 239000010405 anode material Substances 0.000 abstract description 4
- 150000001875 compounds Chemical class 0.000 abstract description 3
- 239000002253 acid Substances 0.000 abstract description 2
- 150000007513 acids Chemical class 0.000 abstract description 2
- 125000003118 aryl group Chemical group 0.000 abstract description 2
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000013078 crystal Substances 0.000 description 3
- 238000002484 cyclic voltammetry Methods 0.000 description 3
- 229910001449 indium ion Inorganic materials 0.000 description 3
- PSCMQHVBLHHWTO-UHFFFAOYSA-K indium(iii) chloride Chemical compound Cl[In](Cl)Cl PSCMQHVBLHHWTO-UHFFFAOYSA-K 0.000 description 3
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 2
- 238000000627 alternating current impedance spectroscopy Methods 0.000 description 2
- 239000013256 coordination polymer Substances 0.000 description 2
- 229920001795 coordination polymer Polymers 0.000 description 2
- 238000002050 diffraction method Methods 0.000 description 2
- ZHUXMBYIONRQQX-UHFFFAOYSA-N hydroxidodioxidocarbon(.) Chemical group [O]C(O)=O ZHUXMBYIONRQQX-UHFFFAOYSA-N 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000011368 organic material Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000006479 redox reaction Methods 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 241000208340 Araliaceae Species 0.000 description 1
- MHABMANUFPZXEB-UHFFFAOYSA-N O-demethyl-aloesaponarin I Natural products O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=C(O)C(C(O)=O)=C2C MHABMANUFPZXEB-UHFFFAOYSA-N 0.000 description 1
- 235000005035 Panax pseudoginseng ssp. pseudoginseng Nutrition 0.000 description 1
- 235000003140 Panax quinquefolius Nutrition 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000005557 chiral recognition Methods 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 229940113088 dimethylacetamide Drugs 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 235000008434 ginseng Nutrition 0.000 description 1
- 230000003760 hair shine Effects 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/003—Compounds containing elements of Groups 3 or 13 of the Periodic Table without C-Metal linkages
-
- 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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
-
- 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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
-
- 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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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- General Chemical & Material Sciences (AREA)
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- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
Abstract
Application the invention discloses two kinds of indiums-aromatic carboxylic acids porous coordination and preparation method thereof and in lithium ion battery, the structural unit of the complex are Ina(L)b(Sol)c, L is the tetrabasic carboxylic acid ligand quadrivalent anion for sloughing hydrogen atom on four carboxyls, Sol N in formula, N- diethylformamide, a=5, b=5, c=5 or L are the hexacarboxylic acid ligand sexavalence anion for sloughing hydrogen atom on six carboxyls, Sol is n,N-dimethylacetamide, a=3, b=2, c=3.The present invention is using aromatic polycarboxylic acids class compound as ligand, indium-aromatic carboxylic acids porous coordination is prepared using solvent-thermal method, preparation method is simple, gained complex has good cyclical stability, excellent electrochemical reversibility and structural stability and high charging and discharging capacity as anode material for lithium-ion batteries.
Description
Technical field
The invention belongs to main group metal organic coordination compound technical fields, and in particular to have preferable electrochemistry to a kind of
Indium-aromatic carboxylic acids porous coordination of energy and the preparation method of the complex and the application in lithium ion battery.
Background technique
Coordination polymer is a kind of most promising crystalline material, with general independent inorganic, organic material phase
Than, coordination polymer will be combined togather the characteristics of both organic ligand and inorganic metal ion with property, make it have with
Independent novel structure and performance inorganic, organic material is different.Due to its structure diversity, property is rich and varied, in gas point
Son and the absorption of small molecule organic vapor with separate, heterogeneous catalysis, multi-phase separation, molecule and ion exchange, chiral Recognition and divide
It from, molecule magnetic property, shines and nonlinear optical property etc. is with a wide range of applications, in the recent period initiation chemical research person
Extensive concern, it is positive to rapidly develop and become the research hotspot in material, the energy and life science crossing domain.
Summary of the invention
The object of the present invention is to provide two kinds of indium-aromatic carboxylic acids porous coordinations with chemical property, and match for this
It closes object and a kind of preparation method and new application is provided.
For above-mentioned purpose, the structural unit of complex of the present invention is Ina(L)b(Sol)c, L is to slough in formula
The tetrabasic carboxylic acid ligand quadrivalent anion of hydrogen atom on four carboxyls, Sol N, N- diethylformamide, a=5, b=5, c=5；
It belongs to rhombic system, Pbcn space group, and cell parameter a isB is C isα is 90 °, and β is 90 °, and γ is 90 °；Or L is the hexacarboxylic acid ligand sexavalence for sloughing hydrogen atom on six carboxyls
Anion, Sol are n,N-dimethylacetamide, a=3, b=2, c=3；It belongs to anorthic system, R-3c space group, structure cell ginseng
Counting a isB isC is α is 90 °, and β is 90 °, and γ is 120 °.
The structural formula of above-mentioned tetrabasic carboxylic acid ligand is as follows:
The structural formula of above-mentioned hexacarboxylic acid ligand is as follows:
The structural unit In of above-mentioned complexa(L)b(Sol)cIn, L is to slough the tetrabasic carboxylic acid of hydrogen atom on four carboxyls to match
Body quadrivalent anion, Sol N, N- diethylformamide, when a=5, b=5, c=5, the complex the preparation method comprises the following steps: by four
Carboxylic acid ligand, inidum chloride are that N is added in 1:1~1.5 in molar ratio, and N- diethylformamide, water, hydrochloric acid volume ratio are 3~3.5:
It in the mixed liquor of 0.75:0.15, stirs evenly, 115~120 DEG C of constant temperature stand reaction 24~30 hours, system in confined conditions
For at indium-aromatic carboxylic acids porous coordination.
The structural unit In of above-mentioned complexa(L)b(Sol)cIn, L is to slough the hexacarboxylic acid of hydrogen atom on six carboxyls to match
Body sexavalence anion, Sol are n,N-dimethylacetamide, when a=3, b=2, c=3, the complex the preparation method comprises the following steps: by six
Carboxylic acid ligand, inidum chloride be in molar ratio 1:8~8.5 DMAC N,N' dimethyl acetamide is added, acetonitrile, hydrochloric acid volume ratio be 3~
It in the mixed liquor of 3.5:1:0.1, stirs evenly, 120~130 DEG C of constant temperature stand reaction 72~78 hours, system in confined conditions
For at indium-aromatic carboxylic acids porous coordination.
Complex of the present invention can be used as lithium electricity positive electrode in lithium ion battery.
It is porous that using aromatic polycarboxylic acids class compound as ligand, using solvent-thermal method indium-aromatic carboxylic acids is prepared in the present invention
Complex, preparation method is simple, and gained complex has good cyclical stability, excellent as anode material for lithium-ion batteries
Electrochemical reversibility and structural stability and high charging and discharging capacity.Under the current density of 20mA/g, have
High charging and discharging capacity, cycle charge-discharge 100 still can achieve 120mAh/g after enclosing, which is more than to be reported at present
Most porous materials.
Detailed description of the invention
Fig. 1 is indium-aromatic carboxylic acids porous coordination crystal structure figure prepared by embodiment 1.
Fig. 2 is indium-aromatic carboxylic acids porous coordination tomograph prepared by embodiment 1.
Fig. 3 is indium-aromatic carboxylic acids porous coordination crystal structure figure prepared by embodiment 2.
Fig. 4 is indium-aromatic carboxylic acids porous coordination tomograph prepared by embodiment 2.
Fig. 5 is indium-cyclic voltammetry curve of the aromatic carboxylic acids porous coordination as lithium electricity positive electrode prepared by embodiment 1
Figure.
Fig. 6 is indium-ac impedance spectroscopy of the aromatic carboxylic acids porous coordination as lithium electricity positive electrode prepared by embodiment 1
Figure.
Fig. 7 be embodiment 1 prepare indium-aromatic carboxylic acids porous coordination as lithium electricity positive electrode 20mA/g electric current
The change curve of stable circulation linearity curve and corresponding coulombic efficiency under density.
Fig. 8 be embodiment 1 prepare indium-aromatic carboxylic acids porous coordination as lithium electricity positive electrode 20mA/g electric current
Charging and discharging curve corresponding with Fig. 8 under density.
Fig. 9 be embodiment 1 prepare indium-aromatic carboxylic acids porous coordination as lithium electricity positive electrode in different current densities
Under high rate performance curve and corresponding coulombic efficiency change curve.
Figure 10 is that indium-aromatic carboxylic acids porous coordination prepared by embodiment 2 is bent as the cyclic voltammetric of lithium electricity positive electrode
Line chart.
Figure 11 is indium-ac impedance spectroscopy of the aromatic carboxylic acids porous coordination as lithium electricity positive electrode prepared by embodiment 2
Figure.
Figure 12 be embodiment 2 prepare indium-aromatic carboxylic acids porous coordination as lithium electricity positive electrode 20mA/g electricity
The change curve of stable circulation linearity curve and corresponding coulombic efficiency under current density.
Figure 13 be embodiment 2 prepare indium-aromatic carboxylic acids porous coordination as lithium electricity positive electrode 20mA/g electricity
Charging and discharging curve corresponding with Figure 13 under current density.
Figure 14 is that indium-aromatic carboxylic acids porous coordination prepared by embodiment 2 is close in different electric currents as lithium electricity positive electrode
The change curve of high rate performance curve and corresponding coulombic efficiency under degree.
Specific embodiment
The present invention is described in more detail with reference to the accompanying drawings and examples, but protection scope of the present invention is not limited only to
These embodiments.
Embodiment 1
It is In with preparation structure unit5(L)5(Sol)5Indium-aromatic carboxylic acids porous coordination for, wherein L be slough four
Tetrabasic carboxylic acid ligand (the H of hydrogen atom on a carboxyl4L4A) quadrivalent anion, Sol N, N- diethylformamide, specific preparation method
It is as follows:
By 0.023g (0.1mmol) InCl3, 0.036g (0.1mmol) tetrabasic carboxylic acid ligand be added 3.9mL N, N- diethyl
Formamide, water, hydrochloric acid volume ratio be 3:0.75:0.15 mixed liquor in, stir evenly, 120 DEG C of constant temperature are quiet in confined conditions
After setting reaction 1 day, cooled to room temperature is prepared into indium-aromatic carboxylic acids porous coordination, calculates yield according to In and is about
40%.
For prepared indium-aromatic carboxylic acids porous coordination mono-crystalline structures as shown in Figure 1, belonging to rhombic system, Pbcn is empty
Between group, cell parameter a isB isC isα is 90 °, and β is 90 °, and γ is
90 °, there are the three independent In of crystallography (III) ions and three L in separate unit4ALigand molecular.In1, In2 and In3 are equal
Eight-coordinate mode is taken, and all is coordinated to form [In (COO) with eight carboxyl oxygen atoms on four ligands4] inorganic secondary structure
Unit, In-O bond distance existBetween, bond angle centered on metal indium ion 55.6 (2)~
Between 165.1 (4) °.From Figure 2 it can be seen that prepared indium-aromatic carboxylic acids porous coordination is three-dimensional net structure.
Embodiment 2
It is In with preparation structure unit3(L)2(Sol)3Indium-aromatic carboxylic acids porous coordination for, wherein L be slough six
Hexacarboxylic acid ligand (the H of hydrogen atom on a carboxyl6L6) sexavalence anion, Sol is n,N-dimethylacetamide, specific preparation method
It is as follows:
By 0.060g (0.28mmol) InCl34.1mLN, N- diformazan is added with 0.020g (0.035mmol) hexacarboxylic acid ligand
Yl acetamide, acetonitrile, hydrochloric acid volume ratio be 3:1:0.1 mixed liquor in, stir evenly, 130 DEG C of constant temperature are quiet in confined conditions
Reaction 3 days is set, indium-aromatic carboxylic acids porous coordination is prepared into, calculating yield according to In is about 53%.
For prepared indium-aromatic carboxylic acids porous coordination mono-crystalline structures as shown in figure 3, belonging to anorthic system, R-3c is empty
Between group, cell parameter a isB isC isα is 90 °, and β is 90 °,
γ is 120 °, and there are the independent In of crystallography (III) ion and a L in separate unit6Ligand molecular.Each crystal
Learn independent metal indium ion and take eight-coordinate mode, on four ligands eight carboxyl oxygen atom O1A, O3A, O1B,
O3B, O2, O4, O2C, O4C are coordinated to form [In (COO)4] the inorganic secondary structure unit of tetrahedral, In-O bond distance existsBetween, the bond angle centered on metal indium ion is between 57.2 (3)~167.0 (3) °.By
Fig. 4 is as it can be seen that prepared indium-aromatic carboxylic acids porous coordination is three-dimensional net structure.
Embodiment 3
Application of the complex of Examples 1 and 2 preparation as lithium electricity positive electrode in lithium ion battery
Indium-virtue of Examples 1 and 2 preparation is carried out using heavy-duty battery detection system and CHI600E electrochemical workstation
Electrochemical Properties of the fragrant carboxylic acid porous coordination as lithium electricity positive electrode, are as a result shown in Fig. 5~14.
As seen from Figure 5, the complex that prepared by embodiment 1 is respectively present two as lithium electricity positive electrode in charge and discharge process
A oxidation peak (within the scope of 0.2-0.7V and 0.7-1.4V) and a reduction peak (within the scope of 0.6-1.4V), from cyclic voltammetry curve
Registration can be seen that its redox reaction with high reversible.As seen from Figure 6, the complex that prepared by embodiment 1 is made
It is made of the semicircle for representing high frequency and intermediate frequency with the oblique line for representing low frequency for the electrochemical impedance curve of lithium electricity positive electrode.By scheming
7 as it can be seen that embodiment 1 prepare complex as lithium electricity positive electrode under 20mA/g current density, as cycle-index increases
Its charging and discharging capacity gradually tends towards stability after being reduced before this.It is enclosed from the 10th circle up to the 100th, charging and discharging capacity
120mAh/g or so is maintained always, and its coulombic efficiency is also maintained essentially at 100% or so, does not all become significantly
Change, this indicates that complex prepared by embodiment 1 has extraordinary cyclical stability as lithium electricity positive electrode.It can by Fig. 8
To see, as the cycle progresses as lithium electricity positive electrode, charging and discharging curve essentially coincides complex prepared by embodiment 1,
Its good stable circulation performance is confirmed.As seen from Figure 9, the complex that prepared by embodiment 1 exists as lithium electricity positive electrode
Under 20mA/g, 40mA/g and 100mA/g current density, each cycle charge-discharge 10 times, charging and discharging capacity is respectively 125mAh/
G, 115mAh/g and 105mAh/g.When current density revert to 20mA/g again, specific capacity has also returned to 125mAh/g, and its
Coulombic efficiency 40mA/g and 100mA/g and during turn again to 20mA/g close to 100%, show that embodiment 1 is made
Standby complex has excellent high rate performance, i.e., good electrochemical reversibility as lithium electricity positive electrode under curent change
And structural stability.It is above-mentioned the experimental results showed that, complex prepared by embodiment 1 is as anode material for lithium-ion batteries with good
Good cyclical stability, excellent electrochemical reversibility and structural stability and high charging and discharging capacity.
As seen from Figure 10, the complex that prepared by embodiment 2 is respectively present in charge and discharge process as lithium electricity positive electrode
Two oxidation peaks (within the scope of 0.1-0.8V and 0.8-2.0V) and a reduction peak (within the scope of 0.4-1.3V), cyclic voltammetry curve
Registration can be seen that its redox reaction with high reversible.As seen from Figure 11, complex conduct prepared by embodiment 2
The electrochemical impedance curve of lithium electricity positive electrode is made of the semicircle for representing high frequency and intermediate frequency with the oblique line for representing low frequency.By Figure 12
As it can be seen that embodiment 2 prepare complex as lithium electricity positive electrode under 20mA/g current density, as cycle-index increases,
Its charging and discharging capacity gradually tends towards stability after being reduced before this, and from the 50th circle up to enclosing its charge and discharge specific volume to the 300th
Amount does not all change significantly, and maintains 120mAh/g or so always, and coulombic efficiency is also maintained essentially at 100% or so,
The complex for demonstrating the preparation of embodiment 2 has preferable cyclical stability as lithium electricity positive electrode.As seen from Figure 13, implement
As the cycle progresses as lithium electricity positive electrode, charging and discharging curve essentially coincides complex prepared by example 2, and has also confirmed it
Good stable circulation performance.As seen from Figure 14, embodiment 2 prepare complex as lithium electricity positive electrode 20mA/g,
Under 40mA/g and 100mA/g current density, each cycle charge-discharge 10 times, charging and discharging capacity be respectively 125mAh/g,
107mAh/g and 100mAh/g.When current density revert to 20mA/g again, specific capacity becomes 105mAh/g, whole process
Coulombic efficiency is all larger than 100%, and it is excellent to show that the complex of the preparation of embodiment 2 has under curent change as lithium electricity positive electrode
Different high rate performance, i.e., good electrochemical reversibility and structural stability.It is above-mentioned the experimental results showed that, embodiment 2 prepare
Complex has good cyclical stability, excellent electrochemical reversibility and stable structure as anode material for lithium-ion batteries
Property and high charging and discharging capacity.
Claims (4)
1. two kinds of indiums-aromatic carboxylic acids porous coordination, it is characterised in that: the structural unit of the complex is Ina(L)b(Sol)c；
L is the tetrabasic carboxylic acid ligand quadrivalent anion for sloughing hydrogen atom on four carboxyls, Sol N, N- diethylformamide, a in formula
=5, b=5, c=5；It belongs to rhombic system, Pbcn space group, and cell parameter a is B is
C isα is 90 °, and β is 90 °, and γ is 90 °；Wherein the structural formula of the tetrabasic carboxylic acid ligand is as follows:
Or L is the hexacarboxylic acid ligand sexavalence anion for sloughing hydrogen atom on six carboxyls, Sol is n,N-dimethylacetamide, a
=3, b=2, c=3；It belongs to anorthic system, R-3c space group, and cell parameter a is B isC isα is 90 °, and β is 90 °, and γ is 120 °；The wherein knot of the hexacarboxylic acid ligand
Structure formula is as follows:
2. a kind of indium of claim 1-aromatic carboxylic acids porous coordination preparation method, the structural unit of the complex is In5
(L)5(Sol)5, L is the tetrabasic carboxylic acid ligand quadrivalent anion for sloughing hydrogen atom on four carboxyls, Sol N, N- diethyl first in formula
Amide, a=5, b=5, c=5, it is characterised in that: by tetrabasic carboxylic acid ligand, inidum chloride be in molar ratio 1:1~1.5 be added N, N-
Diethylformamide, water, hydrochloric acid volume ratio be 3~3.5:0.75:0.15 mixed liquor in, stir evenly, in confined conditions
115~120 DEG C of constant temperature stand reaction 24~30 hours, are prepared into indium-aromatic carboxylic acids porous coordination.
3. a kind of indium of claim 1-aromatic carboxylic acids porous coordination preparation method, the structural unit of the complex is In3
(L)2(Sol)3, L is the hexacarboxylic acid ligand sexavalence anion for sloughing hydrogen atom on six carboxyls, Sol N, N- dimethyl second in formula
Amide, a=3, b=2, c=3, it is characterised in that: by hexacarboxylic acid ligand, inidum chloride be in molar ratio 1:8~8.5 be added N, N-
Dimethyl acetamide, acetonitrile in the mixed liquor that hydrochloric acid volume ratio is 3~3.5:1:0.1, stir evenly, in confined conditions 120
~130 DEG C of constant temperature stand reaction 72~78 hours, are prepared into indium-aromatic carboxylic acids porous coordination.
4. indium described in claim 1-purposes of the aromatic carboxylic acids porous coordination in lithium ion battery as lithium electricity positive electrode.
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Citations (1)
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|---|---|---|---|---|
| CN109400634A (en) * | 2018-11-30 | 2019-03-01 | 陕西师范大学 | The application of 2,5- dihydric para-phthalic acid's indium complex and preparation method thereof and fluorescence detection hydrazine hydrate |
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