CN107768652A - A kind of lithium sulfur battery anode material based on middle micro-diplopore metal oxide or spinelle and preparation method thereof - Google Patents
A kind of lithium sulfur battery anode material based on middle micro-diplopore metal oxide or spinelle and preparation method thereof Download PDFInfo
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- CN107768652A CN107768652A CN201711013615.8A CN201711013615A CN107768652A CN 107768652 A CN107768652 A CN 107768652A CN 201711013615 A CN201711013615 A CN 201711013615A CN 107768652 A CN107768652 A CN 107768652A
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- 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
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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
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
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Abstract
The present invention is by metal organic frame, including HKUST 1, MOF 5, the grade of ZIF 8, ZIF 9, ZIF 67 passes through the method for high temperature pyrolysis, metal oxide or spinel particle with porous skeleton structure is made, the particle is made up of nanoscales time grade particles, then compound with sulphur, that is, obtains lithium sulfur battery anode material.The lithium sulfur battery anode material that preparation method of the present invention is simple, cost is low, prepares has the level cavernous structure that mesopore and micropore are formed, and it is mutually communicated between pore structure, more elemental sulfurs can be adsorbed, it can effectively suppress " the shuttle effect " of more sulphion intermediate products in the electrolytic solution simultaneously, be advantageous to improve the cyclical stability of lithium-sulfur cell.
Description
Technical field
The present invention relates to field of electrochemical batteries, relates more specifically to a kind of lithium sulfur battery anode material and its preparation side
Method.
Background technology
In recent years, with the continuous progress of science and technology, the fast development of various electronic products, it is desirable to electrochmical power source tool used
There is the features such as light weight, small volume, big capacity.Active electrode material based on light element, polyelectron " conversion reaction " is structure
The basis of high-energy density secondary battery system.Using lithium metal as negative pole, elemental sulfur or sulfenyl composite are as positive pole structure
The transfer of 2 electronics is occurring can to realize during complete conversion reaction for the lithium-sulfur cell system built, and its theoretical energy density is up to
2600 watt-hours/kilogram.And sulphur rich content, cheap, environmentally safe close friend in nature, therefore sulphur positive pole turns into
One of most promising positive electrode of lithium battery.Although sulphur just has plurality of advantages, lithium-sulfur cell is current
Also be faced with the problem of some are serious, due to series reaction intermediate can be generated during discharge and recharge reaction --- more sulphur from
Son, these more sulphions include the low Li of the high more sulphions of solubility and solubility2S2And Li2S, the high more sulphur of solubility from
Serious shuttle effect can occur when battery charges for son, and insoluble product can then be deposited on both positive and negative polarity outer surface, cause to live
Property sulphur constantly loses, and efficiency for charge-discharge is not high.Some serial work have been done to suppress more in order to solve these Study on Problems persons
The diffusion mobility of sulphion, improve the cycle performance and efficiency for charge-discharge of lithium-sulfur cell.
The study hotspot of Lithium-sulphur battery anode material is mainly grouped as three major types, and the first kind is with various pattern conductive carbons
Material is carbon/sulphur composite prepared by skeleton, and such as using CNT, graphene, mesoporous carbon storage sulphur, sulphur is limited in into carbon
The dissolving of more lithium sulfides is limited in the duct of material or using the high specific surface area of carbon material, in favor of suppress shuttle effect and
Improve battery performance；Second class is using conducting polymer cladding elemental sulfur or utilizes conducting polymer network skeleton absorption simple substance
Sulphur, the memory bank of polypyrrole, polyaniline, polythiophene as sulphur is such as used, the dissolving of more lithium sulfides can not only be limited, led simultaneously
The activity of electric polymer in itself can also improve the performance of battery；3rd class is by adding metal oxide or metal organic frame
Oxide/sulphur composite is prepared to coat sulphur, can substantially adsorb more lithium sulfides, and then reduces shuttle effect to cell performance
The influence of energy.Wherein, metal oxide fixes more sulphions by chemisorption, and suction-operated is notable, can be one
Determine to reduce influence of the shuttle effect to battery performance in degree.
Such as the existing patents of publication number CN104143630A disclose and metal oxide nano are with the addition of in positive electrode
Pipe, preferably alleviate the dissolution of polysulfide, improve the performance of lithium-sulfur cell to a certain extent.
But at present in lithium-sulphur cell positive electrode, obtained metal oxide carrier specific surface area is small, and pore structure is few,
It is unfavorable for suppressing the dissolution of polysulfide；Meanwhile the carrier of the pattern such as nanotube, nanometer sheet, nano particle is in charge and discharge process
Middle structural stability is poor, and easily deformation is broken or condenses together, and reduces the utilization rate of active material sulphur, has a strong impact on battery
Cyclical stability.
The content of the invention
Present invention aims at a kind of lithium sulfur battery anode material is provided, there is certain size and abundant duct knot
Structure, more elemental sulfurs can be loaded, while effectively suppress " the shuttle effect " of sulphur simple substance and more sulphions in electrolyte, so
Be advantageous to the cycle performance of lithium-sulfur cell, and keep high active material utilization.
The invention provides a kind of metal oxide with high-specific surface area prepared based on metal organic frame precursor
Or spinelle, and in this, as carrier, prepare lithium sulfur battery anode material, significantly suppress " the shuttle effect " of more lithium sulfides,
The utilization rate of sulphur is improved, has obtained superior chemical property.
The invention provides a kind of lithium sulfur battery anode material, and it is compound by metal oxide or spinel carrier and sulphur
Forming, the metal oxide or spinelle are made by metal organic frame precursor by high-temperature calcination, and by nano level
Secondary granule is formed.
In one embodiment of the invention, the metal organic frame precursor is selected from HKUST-1, MOF-5, Cu-
One or more in Co-ZIF, ZIF-8, ZIF-9 or ZIF-67.The metal machine frame precursor can pass through suitable method system
It is standby.In one embodiment of the invention, the metal machine frame precursor is prepared by solution reaction, and preparation method is simple,
It is organic in large-scale production.
In one embodiment of the invention, wherein the metal oxide or spinel carrier are stable polyhedron
Structure.The metal oxide or spinel carrier have a high-specific surface area, and pore volume is big.Due to different metal organic frames
Precursor has different pore passage structures and aperture, causes the metal oxide after calcination to go out also to have different pore passage structures and hole
Footpath, therefore, by selecting different metal organic frame precursors, pore passage structure and aperture can be regulated and controled.Also, because metal has
Machine frame precursor has the multi-stage artery structure of middle micro-diplopore, and therefore, the metal oxide or spinelle obtained after calcining is kept
Original pattern, also show as the multi-stage artery structure of middle micro-diplopore.The carrier granular is made up of nanoscales time grade particles.
In one embodiment of the invention, it is in metal oxygen that the metal oxide or spinel carrier are compound with sulphur
Sulphur is impregnated in compound or spinel carrier.
Present invention also offers a kind of method for preparing lithium sulfur battery anode material, it comprises the following steps：
1) metal organic frame precursor is prepared；
2) metal organic frame precursor described in high-temperature calcination, metal oxide or spinelle are obtained；
3) it is the metal oxide or spinelle and sulphur is compound；
In one embodiment of the invention, preparing the method for lithium sulfur battery anode material is also included step 3) institute
The mixture obtained reacts in a kettle under inert gas shielding, 150-200 DEG C of reaction temperature, and the reaction time is that 4-48 is small
When, preferably 8-40 hours, preferably 10-30 hours, preferably 12-20 hours.The reactor provides the ring of a HTHP
Border, elemental sulfur is in molten state, be diffused into the pore passage structure of metal oxide or spinelle, it is dispersed.
In a kind of embodiment of the method for preparing lithium sulfur battery anode material of the present invention, the metal organic frame
One or more of the precursor in HKUST-1, MOF-5, Cu-Co-ZIF, ZIF-8, ZIF-9 or ZIF-67, preferably by molten
It is prepared by liquid reaction method.
In a kind of embodiment of the method for preparing lithium sulfur battery anode material of the present invention, the calcination is not equality of temperature
Carried out under degree and different atmosphere, as long as stable polyhedron metal oxide or spinelle can be obtained, it is preferable that the calcination
Carried out under inertia or non-inert atmosphere at 500-1000 DEG C, preferably 500-900 DEG C, at a temperature of more preferably 500-800 DEG C
Carry out, the calcination time can be such as 0.5-20 hours, preferably 1-15 hours, more preferably 2-10 hours.
The present invention the method for preparing lithium sulfur battery anode material a kind of embodiment in, step 3) it is compound be
Sulphur is impregnated in metal oxide or spinel carrier.Preferably, wherein dipping sulphur is to be immersed in metal oxide or spinelle
In the organic solution of sulphur, and then it is dried.
Specifically, the present invention can realize by the following technical solutions：
1st, metal organic frame presoma is prepared.Different metal organic framework compounds is prepared using solution reaction method,
Including HKUST-1, MOF-5, Cu-Co-ZIF, ZIF-8, ZIF-9, ZIF-67 etc.；
2nd, metal oxide or spinelle is made in high-temperature calcination.At different temperature, metal is calcined under different atmosphere
Have and add frame precursor, obtain the metal oxide or spinelle of different polyhedral structures；
3rd, composite sulfur.By obtained metal oxide or spinelle in the S/CS that concentration is 5~50mg/mL2Soaked in solution
Stain 5~30 minutes, dried 6~24 hours at a temperature of 40~80 DEG C.Gained mixture is put into instead under argon atmosphere
Answer in kettle, 150~200 DEG C are reacted 4~48 hours.
The present invention has the advantage that：
1st, the stability (polyhedral structure) of carrier structure；
2nd, metal oxide or spinelle have chemisorption to more sulphions；
3rd, the pore volume with high surface area can improve the load capacity of active material sulphur；
4th, the pore passage structure that can regulate and control plays the role of physics confinement to more sulphions；
5th, charging and discharging capacity is improved, obtains stable cycle performance；
6th, preparation method is simple, diameter of carrier, aperture all can artificial regulatory, beneficial to large-scale production.
Brief description of the drawings
Fig. 1 is the scanning electron microscope (SEM) photograph (SEM) for the cupric oxide prepared by metal organic frame precursor that embodiment 1 obtains；
Fig. 2 is cycle performance curve of the obtained lithium-sulfur cell of embodiment 1 under 0.2C multiplying powers；
Fig. 3 is charging and discharging curve of the obtained lithium-sulfur cell of embodiment 1 under 0.2C multiplying powers.
Embodiment
The present invention based on metal organic frame precursor prepare with bigger serface and with the gold of specific pore passage structure
Belong to oxide or spinelle (it is the multi-stage artery structure of middle micro-diplopore), the scope of specific surface area is 500-1500m2g-1, lead to
The double restriction effects of physical chemistry to lithium-sulfur cell intermediate product polysulfide are crossed, obtain excellent chemical property.
Following examples are the further explanations to the present invention, rather than limit the protection domain of invention.
Embodiment 1
HKUST-1 preparation
2.0g trimesic acids and 4.1g copper nitrates are dissolved in the mixing of 100mL N,N-dimethylformamides, second alcohol and water
Solution (volume ratio 1:1:1) in, 85 DEG C are reacted 20 hours.After being down to room temperature, centrifugation, washed with methanol or ethanol.Resulting solution
It is dried in vacuo 12 hours at 150 DEG C, obtains HKUST-1 powder precursors.
CuO preparation
It will be calcined 3 hours at obtained HKUST-1 powder precursors in air atmosphere 900 DEG C, obtain CuO powder.Scanning
Electron microscope (SEM) has the multistage pore canal knot of middle micro-diplopore as shown in figure 1, the carrier is the micron particles of polyhedral structure
Structure, and be made up of nano level secondary granule.
Sulfur loaded
By obtained CuO in the S/CS that concentration is 5mg/mL2Impregnated 5 minutes in solution, it is small that 24 are dried at a temperature of 40 DEG C
When.Gained mixture is put into reactor under argon atmosphere, 155 DEG C are reacted 12 hours.
It is prepared by anode pole piece
Using gained lithium sulfur battery anode material as positive active material, Super-P is conductive agent, PVDF nmp solution
It is binding agent (with mass ratio 8:1:1 mixing).Dried positive electrode and conductive agent are ground 15 minutes in mortar；Grinding is equal
After even, PVDF solution (mass fraction 5%) is proportionally added, is stirred 6 hours on magnetic stirring apparatus；Obtained paste is starched
Liquid is uniformly coated on current collector aluminum foil, on carbon cloth or carbon paper, then dried in 60 DEG C of vacuum drying chamber 20 hours it is standby.
Battery assembles
Electrode after drying is made to a diameter of 12mm circular pole piece；And 30~180 are kept under 8MPa pressure
Second, produce lithium-sulphur cell positive electrode；Using lithium metal as negative pole, Celgard films choose (the trifluoromethyl sulphurs of 1mol/L bis- as barrier film
Sour acyl) imine lithium is electrolyte, 0.4mol/L lithium nitrates make additive, and solvent volume is than DOL (DOX):DME
(glycol dimethyl ether)=1:1, it is assembled into CR2032 type button cells.The addition of electrolyte is 50 times (mass ratioes) of sulphur.
The assembling of whole battery is completed in glove box.
Electrochemical property test
Charge and discharge electrical measurement is carried out to battery using the blue electric LANDCT2001A discharge and recharges instrument of Wuhan Lan Bo Electronics Co., Ltd.s
Examination, charging/discharging voltage scope is 1.5V to 2.8V.Cycle performance test is carried out under 0.2C multiplying powers to it, as a result such as Fig. 2, Fig. 3
And shown in table 1.Under 0.2C multiplying powers, initial capacity reaches 1202mAh/g, still has 836mAh/g after 100 circulations, embodies non-
Often good cycle performance.
Embodiment 2
MOF-5 preparation
0.78g zinc nitrates and 0.166g terephthalic acid (TPA)s are dissolved in 30mL N,N-dimethylformamide solution.Gained
It is put into baking oven, 105 DEG C are reacted 24 hours.After being down to room temperature, washed, centrifuged with DMF, anhydrous chloroform.Institute
Obtain solution to be dried in vacuo 12 hours at 150 DEG C, obtain MOF-5 powder precursors.
ZnO preparation
Obtained MOF-5 powder is calcined 3 hours under air or argon gas atmosphere at 800 DEG C, obtains ZnO powder.
Sulfur loaded
By obtained ZnO in the S/CS that concentration is 5mg/mL2Impregnated 5 minutes in solution, it is small that 12 are dried at a temperature of 40 DEG C
When.Gained mixture is put into reactor under argon atmosphere, 155 DEG C are reacted 12 hours.
Electrode prepares and electro-chemical test
Resulting lithium sulfur battery anode material prepares electrode as implementing 1 and carries out electro-chemical test, electrochemistry
Can result it is as shown in table 1.
Embodiment 3
Cu-Co-ZIF synthesis
The copper nitrate of 1.3g cobalt nitrates and 1.3g is dissolved in 90mL absolute ethyl alcohols (solution A), by 2.9 g 2- methyl
Imidazoles is added in 90mL absolute ethyl alcohols (solution B).B solution is slowly added in solution A, 80 DEG C of stirring in water bath 8 of mixed solution are small
When.Centrifugation, washing, 70 DEG C of dryings.
CuCo2O4Preparation
By obtained Cu-Co-ZIF powder under argon gas or nitrogen atmosphere, calcined 2 hours at 500 DEG C, obtain CuCo2O4
Powder precursor.
Sulfur loaded
The CuCo that will be obtained2O4In the S/CS that concentration is 5mg/mL2Impregnated 5 minutes in solution, 12 are dried at a temperature of 40 DEG C
Hour.Gained mixture is put into reactor under argon atmosphere, 155 DEG C are reacted 12 hours.
Electrode prepares and electro-chemical test
Resulting lithium sulfur battery anode material prepares electrode as implementing 1 and carries out electro-chemical test, electrochemistry
Can result it is as shown in table 1.
Comparative example 1
It is prepared by anode pole piece
It is directly that elemental sulfur is as identical in implemented 1 as positive active material, specific electrode and electro-chemical test.Electrochemistry
Results of property is as shown in table 1.
The embodiment of table 1 and comparative example prepare the electric performance test result of lithium-sulfur cell
As known from Table 1, the specific capacity of lithium-sulfur cell prepared by the embodiment of the present invention 1~3 and cyclical stability are above pair
Ratio 1.Illustrate that metal oxide or spinelle of the present invention based on the preparation of metal organic frame precursor can improve lithium-sulfur cell
Stability, effectively suppress polysulfide in charge and discharge process and dissolve in the electrolytic solution, and reduce polysulfide to lithium anode
Corrosiveness, to realize that lithium-sulfur cell industrialized production lays the foundation.
It is described above, only present pre-ferred embodiments, therefore the scope that the present invention is implemented can not be limited according to this, i.e., according to
The equivalent changes and modifications that the scope of the claims of the present invention and description are made, all should still it belong in the range of the present invention covers.
Claims (10)
1. a kind of lithium sulfur battery anode material, it is to be combined by metal oxide or spinel carrier with sulphur, the metal
Oxide or spinelle are made by metal organic frame precursor by high-temperature calcination, and are made up of nano level secondary granule.
2. positive electrode as claimed in claim 1, the metal organic frame precursor is selected from HKUST-1, MOF-5, Cu-Co-
One or more in ZIF, ZIF-8, ZIF-9 or ZIF-67.
3. positive electrode as claimed in claim 1 or 2, wherein the metal oxide or spinel carrier are stable multiaspect
Body structure.
4. the positive electrode as described in claim any one of 1-3, the metal oxide or spinel carrier is compound with sulphur is
Sulphur is impregnated on metal oxide or spinel carrier.
5. a kind of method for preparing lithium sulfur battery anode material, it comprises the following steps：
1) metal organic frame precursor is prepared；
2) metal organic frame precursor described in high-temperature calcination, metal oxide or spinelle are obtained；
3) it is the metal oxide or spinelle and sulphur is compound.
6. a kind of method for preparing lithium sulfur battery anode material as claimed in claim 5, it also includes will be mixed obtained by step 3)
Compound reacts in a kettle under inert gas shielding, 150-200 DEG C of reaction temperature, and the reaction time is 4-48 hours.
A kind of 7. method that lithium sulfur battery anode material is prepared as described in claim 5 or 6, wherein before the metal organic frame
One or more of the body in HKUST-1, MOF-5, Cu-Co-ZIF, ZIF-8, ZIF-9 or ZIF-67, preferably pass through solution
It is prepared by reaction method.
8. a kind of method that lithium sulfur battery anode material is prepared as described in claim any one of 5-7, wherein the calcination be
Carried out under inertia or non-inert atmosphere at 500-1000 DEG C.
9. a kind of method that lithium sulfur battery anode material is prepared as described in claim any one of 5-8, wherein step 3) is compound
It is to impregnate sulphur on metal oxide or spinel carrier.
A kind of 10. method that lithium sulfur battery anode material is prepared as described in claim any one of 5-9, wherein dipping sulphur is by gold
Category oxide or spinelle are immersed in the organic solution of sulphur, and are then dried.
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