CN106025178A - Method for preparing metal oxide employing MOF as template and application of metal oxide in negative electrode material of lithium battery - Google Patents
Method for preparing metal oxide employing MOF as template and application of metal oxide in negative electrode material of lithium battery Download PDFInfo
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- CN106025178A CN106025178A CN201610390470.2A CN201610390470A CN106025178A CN 106025178 A CN106025178 A CN 106025178A CN 201610390470 A CN201610390470 A CN 201610390470A CN 106025178 A CN106025178 A CN 106025178A
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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
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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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
- H01M4/139—Processes of manufacture
- H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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Abstract
The invention discloses a method for preparing a metal oxide employing an MOF as a template. The method comprises the following steps of: (1) synthesis of an organic ligand H2PBI; (2) synthesis of metal-organic frame complexes (MOFs); and (3) synthesis of a porous metal oxide. Compared with a traditional negative electrode material (graphite) of a lithium-ion battery, the negative electrode material disclosed by the invention has the advantage that the specific capacity is greatly improved, and is improved to 745mAh/g from 372mAh/g after 100 charging and discharging cycles. Compared with the traditional metal oxide as the negative electrode material of the lithium-ion battery, the metal oxide disclosed by the invention has the advantages that the stability is greatly improved and the specific capacity is hardly changed after 100 charging and discharging cycles. Compared with a traditional method for preparing the metal oxide, the preparation method is simpler and more effective.
Description
Technical field
The invention belongs to the application of lithium ion battery negative material, be specifically related to a kind of with MOF as template
The method preparing metal-oxide.
Background technology
Lithium ion battery is owing to having high-energy-density, high output voltage, memory-less effect and non-environmental-pollution etc.
Advantage, is more and more applied.Can be applied not only to various portable electric appts, in conduct
The energy storage device aspect of electric powered motor power supply and the new forms of energy such as solar energy, wind energy has the biggest application prospect.
The current widely used negative pole of business-like lithium ion battery is mainly graphite type material.But graphite theoretical capacity
Low and have safety issue, the highest theoretical capacity, the Novel anode material that safety is good are got more and more
Concern.Oxide cathode material has theoretical capacity height, good cycle, security performance advantages of higher,
It it is the ideal material substituting graphite as lithium ion battery negative.
But, poorly conductive, irreversible capacity be big and before and after discharge and recharge, the problems such as change in volume is big restrict it and obtain
To reality application.
Summary of the invention
Research show the metal-oxide negative material as lithium ion battery, electric conductivity, security performance,
Capacity aspect has good performance, is good lithium ion battery negative material, and the burning of porous
Thing material shows the good electric chemical property such as high power capacity, high stability as the negative material of lithium ion battery.
In the present invention, metal organic frame (MOFs) is a class organic-inorganic hybrid material, is organic ligand
The crystalline material with periodic network structure formed by autonomous dress with metal ion, have high porosity,
The construction featuress such as bigger serface, regular pore canal, skeleton size scalable.MOFs gas absorption separate,
The aspect such as luminescent material, catalytic performance shows good application row performance.Owing to constituting the organic of MOFs
The multiformity of part and plasticity, can design aperture difference MOFs material, by MOFs through high temperature
After calcining, oxygen therein, carbon and nitrogen can be dispelled, thus obtain porous material with carbon element.There are some researches show,
The metal-oxide of porous applies the size of the specific capacity in lithium ion battery negative material to depend on metal oxygen
The kind of compound and aperture.
The invention discloses the preparation method of a kind of height ratio capacity lithium cell cathode material, i.e. with MOF as mould
The method of metal-oxide prepared by plate, comprises the steps:
(1) organic ligand H2The synthesis of PBI；(2) synthesis of metal-organic framework coordination compound (MOFs)；(3)
The synthesis of the metal-oxide of porous；Wherein, described organic ligand H2PBI is
5-(3-Pyridin-3-yl-benzoylamino)-isophthalic acid, i.e. (5-(3-pyridin-3-yl-benzamido)
Isophthalic acid).
Compared with traditional lithium ion battery negative material (graphite), the present invention has the biggest in terms of specific capacity
Raising, through 100 charge and discharge cycles, specific capacity is brought up to 745mAh/g by 372mAh/g, compares
In traditional metal-oxide as lithium ion battery negative material, this invention has the biggest in terms of stability
Improving, through 100 charge and discharge cycles, its specific capacity is almost without change, relative to traditional preparation gold
The method belonging to oxide, this preparation method is simpler, effectively.Due to organic ligand multiformity and can
Design, we can element as required or the content of element, design organic ligand, thus obtain not
Same MOF material, and then obtain the metal-oxide of different pore size kind.
Specifically, in described step (1), organic ligand H2PBI is prepared by following steps:
A. according to 3-bromopyridine: 3-Carboxybenzeneboronic acid: the mol ratio of tetra-triphenylphosphine palladium is 8.786:8.783:
0.5, the most backward first reaction vessel adds 3-bromopyridine, 3-Carboxybenzeneboronic acid and tetra-triphenylphosphine palladium, then
According to the deal of the 3-bromopyridine added, the 3-bromopyridine of every 8.786mmol is corresponding to the first reaction vessel
Add the sodium carbonate liquor 45ml of 0.4mol/L, will reaction heated and stirred under 90 DEG C of oxygen free conditions；Treat anti-
Ying Hou, is cooled to room temperature by the first reaction vessel, and is diluted to pH=1 with dilute hydrochloric acid；Obtain white depositions
And filter at normal temperatures, and wash with water, dry, obtain white solid；
B. gained white solid is added the second reaction vessel, according still further to the part of the 3-bromopyridine that step a is added
Amount, the 3-bromopyridine of every 8.786mmol adds brand-new thionyl chloride 25ml to the second reaction vessel correspondence,
Second reaction vessel refluxes at 80 DEG C, reacts in the most backward second reaction vessel and advertises N2, then obtain
Faint yellow solid；
C. gained faint yellow solid is joined in the 3rd reaction vessel, the 3-bromine pyrrole added according still further to step a
The deal of pyridine, the 3-bromopyridine of every 8.786mmol is corresponding in turn to add DMAc solution to the 3rd reaction vessel
40ml, 5-amino isophthalic acid 8.464mmol and 4-aminopyridine 2.3mmol, stirs under ice-water bath
Mix, obtain milky colloidal solution；
D. gained milky colloidal solution is poured in the 4th reaction vessel holding distilled water, according to step a institute
The deal of the 3-bromopyridine added, the most described distilled water of 3-bromopyridine of every 8.786mmol is 200ml, stirs
Mixing, after reaction completely, filtration under diminished pressure obtains white solid, is described organic ligand H2PBI。
Specifically, described step (2), described metal-organic framework coordination compound MOFs is obtained by following steps
, by the organic ligand H of described step (1)2PBI Yu Mn (NO3)2It is dissolved in C2H5OH and DMF
In solvent, being placed in the reactor of politef by described mixed liquor, in 100 DEG C of temperature ranges, heating is anti-
Ying Santian, is cooled to room temperature and obtains described metal-organic framework coordination compound MOFs.
Specifically, in described step (1), the metal-oxide of described porous is prepared by the following, will
Described metal-organic framework coordination compound MOFs is placed in tube furnace, 900 DEG C of heating 8 under air atmosphere
Hour, both the metal-oxide of described porous.
Preferably, described H2PBI and Mn (NO3)2Mol ratio: 1:(1-2.5).
Preferably, the synthesis of described step (3) porous metal oxide, the control of temperature 500-1100 DEG C
Further, the mixing speed of described step a is 500r/min.
Further, the mixing speed of described step c is 500r/min.
Further, the mixing speed of described step d is 500r/min.
As the scheme of another solution technical problem of the present invention, the burning that said method is prepared into
Thing is as lithium cell cathode material.
Compared with prior art, there is following good effect:
1, the lithium ion battery negative material (graphite) that the present invention is more traditional, specific capacity aspect has the biggest
Improve, through 100 charge and discharge cycles, specific capacity by 372mAh/g bring up to 745mAh/g compared to
Traditional graphite is as lithium ion battery negative material.
2, the present invention improves a lot in terms of stability, through 100 charge and discharge cycles, almost without
Declining, the metal-oxide of other porous relatively, the method for this porous oxide is simpler, effectively.
3, in the present invention, due to multiformity and the designability of organic ligand, we can unit as required
Element or the content of element, design organic ligand, thus obtain different MOF materials, and then obtain difference
The metal-oxide of aperture type.
4, commercial graphite material is as the negative material of lithium ion battery, dashes forward in stability, high rate performance performance
Going out, but its matching is poor, specific capacity (372mAh/g) is the least, it is impossible to meet the need of battery development
Want.And the present invention successfully synthesizes a kind of novel MOFs material, through processing the oxidation obtaining a kind of porous
Thing material, as the negative material of lithium ion battery, successfully improves the specific capacity (745 of lithium ion battery
mAh/g)。
The invention will be further described with embodiment below in conjunction with the accompanying drawings.
Accompanying drawing explanation
Fig. 1 is organic ligand H in the present invention2The synthetic reaction step schematic diagram of PBI.
Fig. 2 is the synthetic reaction step schematic diagram of Mn-MOFs in the present invention.
Fig. 3 is the structural analysis figure of Mn-MOF in the present invention.
Fig. 4 is Mn-MOF structural analysis figure after 900 DEG C of air atmosphere calcinings in the present invention, is that this MOF exists
Under 900 DEG C of air atmosphere, the PXRD after calcining schemes, and five peaks of MnO, say as we can clearly see from the figure
This material bright is the MnO material of porous.
Fig. 5 is the MnO material capacity voltage pattern as lithium ion battery negative material of porous in the present invention.
Fig. 6 is that the MnO material of porous in the present invention is as lithium ion battery negative material charge and discharge cycles figure.
Fig. 7 is that the MnO material of porous in the present invention is as lithium ion battery negative material multiplying power figure.
Detailed description of the invention
The preparation method of the height ratio capacity lithium cell cathode material of the present invention, i.e. with MOF for template preparation gold
The method belonging to oxide, comprises the steps:
As it is shown in figure 1, step (1), organic ligand H2PBI synthesizes, wherein, and described organic ligand H2PBI
For 5-(3-Pyridin-3-yl-benzoylamino)-isophthalic acid, synthesize organic ligand H2PBI by with
Lower step:
A. taking two mouthfuls of flasks of specification 100ml, described two mouthfuls of flasks are the first reaction vessel, to two mouthfuls of flasks
Middle addition 3-bromopyridine 1.388g, 8.786mmol, then in two mouthfuls of flasks, add 3-Carboxybenzeneboronic acid 1.458
G, 8.783mmol, and it is added thereto to tetra-triphenylphosphine palladium 0.578g, 0.5mmol and sodium carbonate liquor 45
Ml, 0.4mol/L, will reaction heated and stirred 10 hours, mixing speed 500r/min under 90 DEG C of oxygen free conditions；
After question response, two mouthfuls of flasks are cooled to room temperature, and are diluted to pH=1 with dilute hydrochloric acid；Obtain white depositions
And filter at normal temperatures, and wash with water, dry, obtain white solid；
B. gained white solid being added flask, described flask is the second reaction vessel, then adds in flask
25ml brand-new thionyl chloride, flask refluxes 8 hours at 80 DEG C, reacts in complete backward flask and advertises N2,
Then faint yellow solid is obtained；
C. being joined by gained faint yellow solid in 100ml single port flask, described single port flask is the 3rd reaction
Container, then in single port flask, it is slowly added into the DMAc solution of 40ml, and add 5-amino isophthalic to it
Dioctyl phthalate 1.532g, 8.464mmol and 4-aminopyridine 0.28g, 2.3mmol, stir 8 under ice-water bath
Hour, mixing speed 500r/min, obtain milky colloidal solution；
D. pouring in the beaker holding 200ml distilled water by gained milky colloidal solution, described beaker is
Four reaction vessels, and be stirred at room temperature 30 minutes, mixing speed 500r/min, after reaction completely, decompression
It is filtrated to get white solid, is described organic ligand H2PBI。
As in figure 2 it is shown, step (2), the synthesis of metal-organic framework coordination compound (MOFs):
By the organic ligand H of 0.018g, 0.05mmol2PBI, 0.0179g, the Mn (NO of 0.05mmol3)2
It is dissolved in 3ml C2H5In the DMF solvent of OH and 3ml, described mixed liquor is placed on politef
In reactor, reacting by heating three days in 100 DEG C of temperature ranges, it is cooled to room temperature and obtains described metal-organic
Frame complex MOFs.
As it is shown on figure 3, the synthesis of step (3) porous metal oxide:
The described metal-organic framework coordination compound MOFs of 2.00g is placed in tube furnace, in air atmosphere
Lower 900 DEG C are heated 8 hours, had both obtained finished product.
Preferably, described step (1) organic ligand H2In the synthesis of PBI, add the 3-carboxyl benzene in flask
The mol ratio of boric acid and 3-bromopyridine is: 1:(0.5-1.5).
Preferably, in the synthesis of described step (2) metal-organic framework coordination compound MOFs, add H2PBI
With Mn (NO3)2Mol ratio: 1:(1-2.5).
As optimizing further: the synthesis of described step (3) porous metal oxide, the control of temperature
500-1100℃。
Such as Fig. 3, the structural analysis figure of Mn-MOF from the present invention, the coordination environment figure of (a) part,
It is a part and six Mn metallic ion coordination；B the tomograph of () MOFs, can be bright in Fig. 3
Show and see that this MOF has two kinds of different one-dimensional channels.
Such as Fig. 4, can in the structural analysis figure after Mn-MOF calcines under 900 DEG C of air atmosphere from the present invention
See, be the PXRD figure after this MOF calcines under 900 DEG C of air, MnO as we can clearly see from the figure
Five peaks, illustrate that this material is the MnO material of porous.
Such as Fig. 5, from the present invention, Mn-MOF material is as the capacity voltage pattern of lithium ion battery negative material
In visible, this material, as lithium ion battery negative material, shows good charge-discharge performance, first
Electric discharge can reach 1450mAh/g, and the charge and discharge platform of this material, at below 2V, has and fills than relatively low
Discharge platform, and platform is more flat, has excellent commercial promise and is well suited as the negative pole of lithium ion battery
Material.
Such as Fig. 6, from the present invention, Mn-MOF material is as lithium ion battery negative material charge and discharge cycles figure
In visible, through the circulation of 100 discharge and recharges, its specific capacity can be stable at about 745mAh/g, its storehouse
Human relations efficiency is higher, shows good chemical property.
Such as Fig. 7, from the present invention, Mn-MOF material is as the multiplying power figure of lithium ion battery negative material,
The metal-oxide of the porous of the present invention has high magnification stability, and cycle performance is excellent.
It should be noted that
Dilute hydrochloric acid, the i.e. mass fraction hydrochloric acid less than 20%.Achromaticity and clarification liquid.Highly acid.Irritant
Abnormal smells from the patient.PH value regulator.
DMAC formal name used at school dimethyl acetylamide, (Dimethylacetamide), molecular formula CH3CON(CH3)2,
Molecular weight: 87.12, No. CAS: 127-19-5.
DMF solvent is dimethylformamide, is the common solvent of chemical reaction.
Specific capacity: be divided into weight ratio capacity and volume and capacity ratio, more be weight ratio capacity (unit
It is mAh/g), refer to the electricity that the battery of Unit Weight or active substance can be released, be that to weigh battery performance good
A bad important symbol.
High rate performance: under different electric current densities (such as 100mA/g, 1000mA/g etc.), battery is carried out
Discharge and recharge, (ratio) amount of capacity that battery is showed, is also the important symbol weighing battery performance quality,
Typically can be along with the rising of charging and discharging currents density, specific capacity can decline.
Cycle performance is tested: refers to, under a certain electric current density, battery is carried out discharge and recharge, sees discharge and recharge number of times pair
The impact of specific capacity.
The invention is not limited in above-mentioned embodiment, if various changes or modification to the present invention are without departing from this
Bright spirit and scope, if these changes and modification belong to claim and the equivalent technologies scope of the present invention
Within, then the present invention is also intended to comprise these change and modification.
Claims (10)
1. the method preparing metal-oxide for template with MOF, it is characterised in that the steps include: that (1) has
Machine part H2The synthesis of PBI；(2) synthesis of metal-organic framework coordination compound MOFs；(3) porous
The synthesis of metal-oxide.
2. the method preparing metal-oxide with MOF for template as claimed in claim 1, it is characterised in that described
In step (1), organic ligand H2PBI is prepared by following steps:
A. according to 3-bromopyridine: 3-Carboxybenzeneboronic acid: the mol ratio of tetra-triphenylphosphine palladium is 8.786:8.783:
0.5, the most backward first reaction vessel adds 3-bromopyridine, 3-Carboxybenzeneboronic acid and tetra-triphenylphosphine palladium, then
According to the deal of the 3-bromopyridine added, the 3-bromopyridine of every 8.786mmol is corresponding to the first reaction vessel
Add the sodium carbonate liquor 45ml of 0.4mol/L, will reaction heated and stirred under 90 DEG C of oxygen free conditions；Treat anti-
Ying Hou, is cooled to room temperature by the first reaction vessel, and is diluted to pH=1 with dilute hydrochloric acid；Obtain white depositions
And filter at normal temperatures, and wash with water, dry, obtain white solid；
B. gained white solid is added the second reaction vessel, according still further to the part of the 3-bromopyridine that step a is added
Amount, the 3-bromopyridine of every 8.786mmol adds brand-new thionyl chloride 25ml to the second reaction vessel correspondence,
Second reaction vessel refluxes at 80 DEG C, reacts in the most backward second reaction vessel and advertises N2, then obtain
Faint yellow solid；
C. gained faint yellow solid is joined in the 3rd reaction vessel, the 3-bromine pyrrole added according still further to step a
The deal of pyridine, the 3-bromopyridine of every 8.786mmol is corresponding in turn to add DMAc solution to the 3rd reaction vessel
40ml, 5-amino isophthalic acid 8.464mmol and 4-aminopyridine 2.3mmol, stirs under ice-water bath
Mix, obtain milky colloidal solution；
D. gained milky colloidal solution is poured in the 4th reaction vessel holding distilled water, according to step a institute
The deal of the 3-bromopyridine added, the most described distilled water of 3-bromopyridine of every 8.786mmol is 200ml, stirs
Mixing, after reaction completely, filtration under diminished pressure obtains white solid, is described organic ligand H2PBI。
3. the method preparing metal-oxide with MOF for template as claimed in claim 1, it is characterised in that: described
In step (2), described metal-organic framework coordination compound MOFs is obtained by following steps, by described
The organic ligand H of step (1)2PBI Yu Mn (NO3)2It is dissolved in C2H5In OH and DMF solvent,
Described mixed liquor is placed in the reactor of politef, reacting by heating three in 100 DEG C of temperature ranges
My god, it is cooled to room temperature and obtains described metal-organic framework coordination compound MOFs.
4. the method preparing metal-oxide with MOF for template as claimed in claim 4, it is characterised in that: described
H2PBI and Mn (NO3)2Mol ratio: 1:(1-2.5).
5. the method preparing metal-oxide with MOF for template as claimed in claim 1, it is characterised in that: described
In step (1), the metal-oxide of described porous is prepared by the following, by described metal-organic
Frame complex MOFs is placed in tube furnace, and under air atmosphere, 900 DEG C are heated 8 hours, both obtain
The metal-oxide of described porous.
6. the method preparing metal-oxide with MOF for template as claimed in claim 5, it is characterised in that: described
The synthesis of step (3) porous metal oxide, the control of temperature 500-1100 DEG C.
7. the method preparing metal-oxide with MOF for template as claimed in claim 2, it is characterised in that: described
The mixing speed of step a is 500r/min.
8. the method preparing metal-oxide with MOF for template as claimed in claim 2, it is characterised in that: described
The mixing speed of step c is 500r/min.
9. the method preparing metal-oxide with MOF for template as claimed in claim 2, it is characterised in that: described
The mixing speed of step d is 500r/min.
10. using the metal-oxide being prepared into of any one of claim 1-9 as lithium cell cathode material.
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| CN106450227A (en) * | 2016-11-24 | 2017-02-22 | 福建师范大学 | Method for preparing lithium batteries by hierarchy In2O3/C composite materials |
| CN107492637A (en) * | 2017-07-18 | 2017-12-19 | 华南师范大学 | A kind of porous carbon blended metal oxide and lithium ion battery prepared therefrom |
| CN108394964A (en) * | 2017-12-26 | 2018-08-14 | 南开大学 | A kind of doping air burns Cu-MOF activated carbon electrodes and its preparation |
| CN109081381A (en) * | 2018-10-11 | 2018-12-25 | 东莞市中航华讯卫星技术有限公司 | Nanoporous negative electrode material Fe3O4Preparation method |
| CN109824028A (en) * | 2019-01-18 | 2019-05-31 | 华南师范大学 | It is a kind of using coordination polymer as the nitrogen-doped porous carbon material of precursor preparation and application |
| CN114314669A (en) * | 2021-12-31 | 2022-04-12 | 杭州电子科技大学 | Lithium ion battery negative electrode material delta-MnO taking MOF as template2Preparation method of (1) |
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|---|---|---|---|---|
| CN106450227A (en) * | 2016-11-24 | 2017-02-22 | 福建师范大学 | Method for preparing lithium batteries by hierarchy In2O3/C composite materials |
| CN106450227B (en) * | 2016-11-24 | 2020-04-03 | 福建师范大学 | Method for preparing lithium battery by using In2O3/C composite material with hierarchical structure |
| CN107492637A (en) * | 2017-07-18 | 2017-12-19 | 华南师范大学 | A kind of porous carbon blended metal oxide and lithium ion battery prepared therefrom |
| CN107492637B (en) * | 2017-07-18 | 2019-10-11 | 华南师范大学 | A kind of porous carbon blended metal oxide and lithium ion battery prepared therefrom |
| CN108394964A (en) * | 2017-12-26 | 2018-08-14 | 南开大学 | A kind of doping air burns Cu-MOF activated carbon electrodes and its preparation |
| CN109081381A (en) * | 2018-10-11 | 2018-12-25 | 东莞市中航华讯卫星技术有限公司 | Nanoporous negative electrode material Fe3O4Preparation method |
| CN109081381B (en) * | 2018-10-11 | 2020-11-13 | 蔚蓝(广东)新能源科技有限公司 | Nano porous negative electrode material Fe3O4Preparation method of (1) |
| CN109824028A (en) * | 2019-01-18 | 2019-05-31 | 华南师范大学 | It is a kind of using coordination polymer as the nitrogen-doped porous carbon material of precursor preparation and application |
| CN114314669A (en) * | 2021-12-31 | 2022-04-12 | 杭州电子科技大学 | Lithium ion battery negative electrode material delta-MnO taking MOF as template2Preparation method of (1) |
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