CN105609767B - One kind contains additive MgxNi(1‑x)O lithium sulfur battery anode material and preparation method - Google Patents
One kind contains additive MgxNi(1‑x)O lithium sulfur battery anode material and preparation method Download PDFInfo
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- CN105609767B CN105609767B CN201610079714.5A CN201610079714A CN105609767B CN 105609767 B CN105609767 B CN 105609767B CN 201610079714 A CN201610079714 A CN 201610079714A CN 105609767 B CN105609767 B CN 105609767B
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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
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/581—Chalcogenides or intercalation compounds thereof
- H01M4/5815—Sulfides
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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
- H01M4/62—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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- 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
Abstract
The invention discloses one kind to contain additive MgxNi(1‑x)O lithium sulfur battery anode material, by MgxNi(1‑x)O and S is entrained in KS 6 lamella, wherein KS 6：S：MgxNi(1‑x)O three's mass ratio is 4：6：0.5~2；MgxNi(1‑x)O is referred to as metal oxide, and 0<x<1.0.The invention also discloses this kind to contain additive MgxNi(1‑x)The preparation method of O lithium sulfur battery anode material.Mg is added in the lithium sulfur battery anode material of the present inventionxNi(1‑x)O, it can be prevented with physical absorption polysulfide and delay polysulfide to be dissolved into electrolyte, can also be catalyzed the fracture of S S keys, so as to improve the cyclical stability of lithium-sulfur cell and coulombic efficiency, is improved battery material chemical property, is extended battery life.
Description
Technical field
The invention belongs to lithium-sulfur cell technical field, is related to one kind and contains additive MgxNi(1-x)O lithium-sulphur cell positive electrode
Material, the invention further relates to this kind to contain additive MgxNi(1-x)The preparation method of O lithium sulfur battery anode material.
Background technology
As new energy technology develops rapidly, the R＆D and promotion of high-energy density secondary battery turns into new energy field
Study hotspot.Conventional lithium ion battery is by positive electrode theoretical discharge specific capacity (LiCoO2、LiNiO2And LiMn2O4Theory put
Electric specific capacity is respectively 274mAh/g, 274mAh/g and 148mAh/g) etc. factor restriction, it is difficult in the field such as the energy and traffic
It is used widely.Lithium-sulfur rechargeable battery then relies on the advantages that its specific capacity is high, security is good, cost is low, environmentally friendly, into
For most one of power supply system of prospect at present.Lithium-sulfur rechargeable battery makees negative pole, elemental sulfur or sulfenyl composite with lithium metal
As positive pole, the theoretical specific capacity of elemental sulfur is 1675mAh/g, and theory is than energy up to 2600Wh/kg, and sulphur also has reserves
The advantages that abundant, cheap and nontoxic.
But the lithium-sulfur cell that elemental sulfur does positive pole is wanted really to move towards practical and there is problems：(1) either
Simple substance S or its reduzate Li2S is insulator, influences the transmission of electric charge；(2)Li2S is poorly reversible, easily loses electrification
Learn activity；(3) due to Li2S and S density difference is larger, positive and negative pole material circulation generation volumetric expansion receipts in charge and discharge process
Contracting, can destroy electrode structure；(4) intermediate product polysulfide be present, it is soluble and to be migrated in the electrolyte to negative pole, cause
Active material loses and larger energy loss.
Nanometer oxide material typically has the characteristics that particle diameter is minimum, specific surface area is very big.Metal oxide is excellent mostly
Good semiconductor, nano-metal-oxide can be introduced into sulphur positive pole by the method for modifying such as loading, filling or coat, improved single
The chemical property of matter sulphur.High-specific surface area and stronger suction-operated due to nano-metal-oxide, after adding sulfur electrode
The dissolving diffusion for suppressing polysulfide can be reached, improve the purpose of the chemical property of lithium-sulfur cell system.
Therefore, nano metal oxide materials and elemental sulfur be compound and an important research of lithium sulfur battery anode material
Direction.KS-6 serves as the carrier and conductive agent of sulphur, adds MgxNi(1-x)After O, the nutty structure of its rough surface can effectively be inhaled
Attached sulphur and more sulphions, slow down shuttle effect, and MgxNi(1-x)O can be catalyzed the fracture of S -- S, can promote the oxygen in lithium-sulfur cell
Change reduction reaction, so as to improve the cyclical stability of lithium-sulfur cell and coulombic efficiency, extend battery life.
The content of the invention
It is an object of the invention to provide one kind to contain additive MgxNi(1-x)O lithium sulfur battery anode material, solve existing
There is the problem of when elemental sulfur is as positive electrode in technology, battery discharge specific capacity is low, poor circulation.
It is a further object of the present invention to provide this kind to contain additive MgxNi(1-x)The preparation of O lithium sulfur battery anode material
Method.
The technical solution adopted in the present invention is that one kind contains additive MgxNi(1-x)O lithium sulfur battery anode material, by
MgxNi(1-x)O and S are entrained in KS-6 lamella, wherein KS-6：S：MgxNi(1-x)O three's mass ratio is 4：6：0.5~2；
MgxNi(1-x)O is referred to as metal oxide, and 0<x<1.0.
Another technical scheme of the present invention is that one kind contains additive MgxNi(1-x)O lithium-sulphur cell positive electrode material
The preparation method of material, implements according to following steps：
Step 1) adds magnesium salts and nickel salt in deionized water, and ultrasonic disperse is completely dissolved it in 10~60 minutes, obtains
Solution A；
Step 2) takes citric acid to add in solution A, and the mass ratio of the total addition level and citric acid of magnesium salts and nickel salt is 1：
0.5~2.5, evaporated in water-bath in 70~90 DEG C of stirrings, until obtaining thick green gel precursors B；
Gel precursors B after 70 DEG C~90 DEG C dryings 24~48 hours, is placed in Muffle furnace by step 3) in air dry oven
In 400 DEG C~800 DEG C calcine 4~8 hours, obtain MgxNi(1-x)O solids；
Step 4) is by KS-6：S：MgxNi(1-x)O is according to mass ratio 4：6：0.5~2 is mixed, and mechanical ball mill is after 2 hours,
It is placed in hydrothermal reaction kettle, after being passed through 20-30 minute argon gas, is incubated 5~20 hours in 155~160 DEG C, obtains MgxNi(1-x)O/
KS-6/S lithium sulfur battery anode materials.
The invention has the advantages that add Mg in the lithium sulfur battery anode material of the present inventionxNi(1-x)O, it can be with physics
Polysulfide is adsorbed, prevents and delays polysulfide to be dissolved into electrolyte, the fracture of S -- S can also be catalyzed, so as to improve
The cyclical stability and coulombic efficiency of lithium-sulfur cell, improve battery material chemical property, extend battery life.The inventive method
Nano level metal oxide Mg is prepared using sol-gel processxNi(1-x)O, processing step is simple, and raw material sources are extensive, into
This is low and reproducible, and Mg is made by ball milling and heat treatmentxNi(1-x)O-KS-6/S lithium sulfur battery anode materials, discharge specific volume
Slower, the good cycling stability of amount decay, can provide basis for the industrialization of lithium-sulfur cell.
Brief description of the drawings
Fig. 1 is Mg prepared by the embodiment of the present invention 10.6Ni0.4O scanning electron microscope (SEM) photograph；
Fig. 2 is Mg prepared by the embodiment of the present invention 10.6Ni0.4O X-ray diffractogram；
Fig. 3 is Mg prepared by the embodiment of the present invention 10.6Ni0.4O-KS-6/S composite positive poles and no added Mg0.6Ni0.4O
First charge-discharge curve of the KS-6/S composite positive poles under 0.1C；
Fig. 4 is Mg prepared by the embodiment of the present invention 10.6Ni0.4O-KS-6/S composite positive poles and no added Mg0.6Ni0.4O
Cycle performance figure of the KS-6/S composite positive poles under 0.1C.
Embodiment
The present invention is described in detail with reference to the accompanying drawings and detailed description.
The present invention contains additive MgxNi(1-x)O lithium sulfur battery anode material, by MgxNi(1-x)O and S are entrained in KS-6
Lamella in, wherein KS-6：S：MgxNi(1-x)O three's mass ratio is 4：6：0.5~2；MgxNi(1-x)O is referred to as metal oxide, and 0
<x<1.0, metal oxide forms for the particle packing of spherical rough surface, and size is 20~100nm.
The present invention contains additive MgxNi(1-x)The preparation method of O lithium sulfur battery anode material, it is real according to following steps
Apply：
Step 1) is by magnesium salts (one or both of magnesium nitrate and magnesium acetate) and nickel salt (one in nickel nitrate and nickel acetate
Kind or two kinds) add deionized water in, ultrasonic disperse is completely dissolved it in 10~60 minutes, obtains solution A；
Step 2) takes citric acid to add in solution A, and the mass ratio of the total addition level and citric acid of magnesium salts and nickel salt is 1：0.5
~2.5, evaporated in water-bath in 70~90 DEG C of stirrings, until obtaining thick green gel precursors B；
Gel precursors B after 70 DEG C~90 DEG C dryings 24~48 hours, is placed in Muffle furnace by step 3) in air dry oven
In 400 DEG C~800 DEG C calcine 4~8 hours, obtain MgxNi(1-x)O solids；
Step 4) is by KS-6：S：MgxNi(1-x)O is according to mass ratio 4：6：0.5~2 is mixed, and mechanical ball mill is after 2 hours,
It is placed in hydrothermal reaction kettle, after being passed through 20-30 minute argon gas, is incubated 5~20 hours in 155~160 DEG C, obtains MgxNi(1-x)O/
KS-6/S lithium sulfur battery anode materials.
The assembling of battery：Lithium sulfur battery anode material, 10wt%~20wt% of the anode sizing agent by 70wt%~80wt%
Conductive agent (KS-6, conductive black, acetylene black) and 10wt%~20wt% binding agent (PVDF) be mixed, solvent N-
Methyl pyrrolidone, uniform pulpous state is modulated into, carries out drying tabletting after coating, positive plate is made in cut-parts；In addition using lithium piece as
Negative plate, electrolyte are containing 1%LiNO31mol/L LiTFSI/DOL-DME (1：1, V%), barrier film Celgard2300,
It is assembled into CR2025 button cells.
Embodiment 1
1) 23.1g magnesium nitrates and 11.6g nickel nitrates are added in 150ml deionized waters, ultrasonic disperse makes its complete in 20 minutes
Fully dissolved, obtain solution A；
2) take 18g citric acids to add in solution A, in water-bath 90 DEG C of stirrings be evaporated up to obtain thick green solidifying
Glue precursor B；
3) gel precursors B after 80 DEG C of dryings 24 hours, is calcined 5 hours for 700 DEG C in Muffle furnace, obtained in air dry oven
To Mg0.6Ni0.4O solids；
4) by KS-6：S：Mg0.6Ni0.4O is according to mass ratio 4：6：1 is mixed, and mechanical ball mill is placed in hydro-thermal after 2 hours
In reactor, after being passed through 20 minutes argon gas, 10 hours are incubated in 156 DEG C, obtains Mg0.6Ni0.4O-KS-6/S composites；
The assembling of battery：Anode sizing agent by 70wt% lithium sulfur battery anode material, 20wt% conductive agent KS-6 and
10wt% binding agent (PVDF) is mixed, and solvent is 1-METHYLPYRROLIDONE, is modulated into uniform pulpous state, is dried after coating
Positive plate is made in dry-pressing piece, cut-parts, and in addition using lithium piece as negative plate, electrolyte is containing 1%LiNO31mol/L LiTFSI/
DOL–DME(1：1, V%), barrier film Celgard2300, CR2025 button cells are assembled into.
Reference picture 1, the Mg prepared for embodiment 10.6Ni0.4O scanning electron microscope (SEM) photographs, pass through sol-gel as can be seen from Figure 1
Mg prepared by method0.6Ni0.4O particle diameters are in 40nm or so, in shaggy spheric granules.
Reference picture 2, the Mg prepared for embodiment 10.6Ni0.4O X-ray diffractogram, all diffraction maximum positions all with standard
Spectrogram JCPDS No.34-0410 match, it was demonstrated that it is Mg to prepare product0.6Ni0.4O。
Reference picture 3, the Mg prepared for embodiment 10.6Ni0.4O-KS-6/S composite positive poles and no added Mg0.6Ni0.4O
First charge-discharge curve of the KS-6/S composite positive poles under room temperature 0.1C multiplying powers.Mg0.6Ni0.4O-KS-6/S anode composites
The first discharge specific capacity of material is 1224mAh/g, longer in 2.1V discharge platforms, and no added Mg0.6Ni0.4O KS-6/S
Composite positive pole first discharge specific capacity is only 676mAh/g, shorter in 2.1V discharge platforms, it was demonstrated that addition Mg0.6Ni0.4O can
To significantly improve the first discharge specific capacity of battery, and discharge platform can be extended.
Reference picture 4, the Mg prepared for embodiment 10.6Ni0.4O-KS-6/S composite positive poles and no added Mg0.6Ni0.4O
Cycle performance figure of the KS-6/S composite positive poles under 0.1C.Mg as can be seen from Figure 40.6Ni0.4O-KS-6/S anode composite materials
Specific discharge capacity 492mAh/g after material circulates 30 times, capability retention 40.2%, no added Mg0.6Ni0.4O KS-6/S is compound
Specific discharge capacity 257mAh/g after positive electrode circulates 30 times, capability retention 38.0%, by contrast, the present embodiment follow
Ring performance is obviously improved.
Embodiment 2
1) 15.4g magnesium nitrates and 17.4g nickel nitrates are added in 150ml deionized waters, ultrasonic disperse makes its complete in 15 minutes
Fully dissolved, obtain solution A；
2) take 17g citric acids to add in solution A, be evaporated up to obtain thick green gel in 70 DEG C of stirrings of water-bath
Precursor B；
3) by gel precursors B after the drying 48 hours of 70 DEG C of air dry oven, calcine 4 hours for 800 DEG C, obtain in Muffle furnace
Mg0.4Ni0.6O；
4) by KS-6：S：Mg0.4Ni0.6O is according to mass ratio 4：6：2 are mixed, and mechanical ball mill is placed in hydro-thermal after 2 hours
In reactor, after being passed through 25 minutes argon gas, 20 hours are incubated in 158 DEG C, produces KS-6/S/Mg0.4Ni0.6O composites.
The assembling of battery：Anode sizing agent by 80wt% lithium sulfur battery anode material, 10wt% conductive agent KS-6 and
10wt% binding agent (PVDF) is mixed, and solvent is 1-METHYLPYRROLIDONE, is modulated into uniform pulpous state, is dried after coating
Positive plate is made in dry-pressing piece, cut-parts, and in addition using lithium piece as negative plate, electrolyte is containing 1%LiNO31mol/L LiTFSI/
DOL–DME(1：1, V%), barrier film Celgard2300, CR2025 button cells are assembled into.
Gained battery 30 cycle charge-discharges under room temperature 0.1C multiplying powers, first discharge specific capacity 1142mAh/g, 30 times
Capacity is maintained at 462mAh/g, capability retention 40.5% afterwards.
Embodiment 3
1) 15g magnesium nitrates and 17g nickel nitrates are added in 150ml deionized waters, ultrasonic disperse makes it completely molten for 45 minutes
Solution, obtains solution A；
2) take 16g citric acids to add in solution A, be evaporated up to obtain thick green gel in 80 DEG C of stirrings of water-bath
Precursor B；
3) by gel precursors B after the drying 36 hours of 80 DEG C of air dry oven, calcine 8 hours for 500 DEG C, obtain in Muffle furnace
Mg0.4Ni0.6O；
4) by KS-6：S：Mg0.4Ni0.6O is according to mass ratio 4：6：1.5 are mixed, and mechanical ball mill is placed in water after 2 hours
In thermal response kettle, after being passed through 30 minutes argon gas, 15 hours are incubated in 160 DEG C, produces KS-6/S/Mg0.4Ni0.6O composites.
The assembling of battery：Anode sizing agent by 80wt% lithium sulfur battery anode material, 10wt% conductive agent KS-6 and
10wt% binding agent (PVDF) is mixed, and solvent is 1-METHYLPYRROLIDONE, is modulated into uniform pulpous state, is dried after coating
Positive plate is made in dry-pressing piece, cut-parts, and in addition using lithium piece as negative plate, electrolyte is containing 1%LiNO31mol/L LiTFSI/
DOL–DME(1：1, V%), barrier film Celgard2300, CR2025 button cells are assembled into.
Gained battery 30 cycle charge-discharges under room temperature 0.1C multiplying powers, first discharge specific capacity 1140mAh/g, 30 times
Capacity is maintained at 463mAh/g, capability retention 40.6% afterwards.
Claims (2)
1. one kind contains additive MgxNi(1-x)The preparation method of O lithium sulfur battery anode material, the lithium sulfur battery anode material
By MgxNi(1-x)O and S are entrained in KS-6 lamella, wherein KS-6：S：MgxNi(1-x)O three's mass ratio is 4：6：0.5~2；
MgxNi(1-x)O is referred to as metal oxide, and 0<x<1.0, described metal oxide size is 20~100nm, it is characterised in that is pressed
Implement according to following steps：
Step 1) adds magnesium salts and nickel salt in deionized water, and ultrasonic disperse is completely dissolved it in 10~60 minutes, obtains solution
A；
Step 2) takes citric acid to add in solution A, and the mass ratio of the total addition level and citric acid of magnesium salts and nickel salt is 1：0.5~
2.5, evaporated in water-bath in 70~90 DEG C of stirrings, until obtaining thick green gel precursors B；
Gel precursors B after 70 DEG C~90 DEG C dryings 24~48 hours, is placed in 400 in Muffle furnace by step 3) in air dry oven
DEG C~800 DEG C calcine 4~8 hours, obtain MgxNi(1-x)O solids；
Step 4) is by KS-6：S：MgxNi(1-x)O is according to mass ratio 4：6：0.5~2 is mixed, and mechanical ball mill is placed in after 2 hours
In hydrothermal reaction kettle, after being passed through 20-30 minute argon gas, 5~20 hours are incubated in 155~160 DEG C, obtains MgxNi(1-x)O/KS-
6/S lithium sulfur battery anode materials.
2. according to claim 1 contain additive MgxNi(1-x)The preparation method of O lithium sulfur battery anode material, it is special
Sign is：Described magnesium salts selects one or both of magnesium nitrate and magnesium acetate；Nickel salt is selected in nickel nitrate and nickel acetate
It is one or two kinds of.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103972580A (en) * | 2013-02-06 | 2014-08-06 | 苏州宝时得电动工具有限公司 | Lithium sulfur battery |
| CN104752702A (en) * | 2015-03-16 | 2015-07-01 | 长沙矿冶研究院有限责任公司 | Cathode material of lithium sulphur battery, preparation method of cathode material, cathode of lithium sulphur battery and lithium sulphur battery |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103972580A (en) * | 2013-02-06 | 2014-08-06 | 苏州宝时得电动工具有限公司 | Lithium sulfur battery |
| CN104752702A (en) * | 2015-03-16 | 2015-07-01 | 长沙矿冶研究院有限责任公司 | Cathode material of lithium sulphur battery, preparation method of cathode material, cathode of lithium sulphur battery and lithium sulphur battery |
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| Title |
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| Effect of nanosized adsorbing material on electrochemical properties of sulfur cathodes for Li/S secondary;Min-Sang Song et al;《Journal of the electrochemical society》;20040630;第151卷(第6期);第A791页实验部分，第A792页右栏第1段 * |
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