CN105406034A - Three-dimensional porous graphene-supported carbon-coated lithium sulfide cathode material as well as preparation method and application thereof - Google Patents
Three-dimensional porous graphene-supported carbon-coated lithium sulfide cathode material as well as preparation method and application thereof Download PDFInfo
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
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- H01M4/362—Composites
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- 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
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- 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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- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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- H—ELECTRICITY
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- H01M4/02—Electrodes composed of, or comprising, active material
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Abstract
The invention discloses a three-dimensional porous graphene-supported carbon-coated lithium sulfide cathode material as well as a preparation method and application thereof. The preparation method comprises the following steps: dispersing oxidized grapheme in water for magnetic stirring, then adding a reducing agent, stirring and dissolving to obtain a brown solution; putting the solution at the temperature of 120-200 DEG C to carry out a hydrothermal reaction for 4-12 h so as to obtain a columnar three-dimensional porous grapheme solution; adding lithium sulfate and a carbon source to the columnar three-dimensional porous grapheme solution to form a columnar three-dimensional porous grapheme soak solution; carrying out freeze drying on the soak solution to obtain a precursor; calcining the precursor for 2-12 h under a protective atmosphere at the temperature of 800-1000 DEG C so as to obtain the three-dimensional porous graphene-supported carbon-coated lithium sulfide material. A battery cathode can be prepared through direct slicing by using the prepared material, the steps of slurry preparation, coating and drying are saved, the technology is simpler, and the material is suitable for large-scale production and has excellent electrical properties.
Description
Technical field
The present invention relates to lithium-sulfur cell Material Field, be specifically related to coated lithium sulfide positive electrode of a kind of three-dimensional porous graphene-supported carbon and its preparation method and application.
Background technology
Environmental problem and energy crisis are current faced two the challenging greatly of human society, and the clean renewable new forms of energy of exploitation have become the active demand of society.Current extensive use be the lithium rechargeable battery of positive pole with embedded type lithium-containing transition metal oxide base (LiMn2O4, cobalt acid lithium, ternary, LiFePO4, the rich lithium LiMn2O4 of stratiform) material, due to the restriction (energy density of current material system is difficult to the energy density bottleneck breaking through 250Wh/kg) of its theoretical capacity, cannot meet at present for the requirement of more high-energy-density power supply.Therefore, the new energy technology researching and developing energy efficient conversion and storage has become the great demand of national energy development strategy.
Lithium-sulfur cell becomes the study hotspot of high-energy density secondary battery of future generation due to its high theoretical capacity.Compared with traditional lithium ion battery, lithium-sulfur cell theoretical specific capacity reaches 1675mAh/g, specific energy reaches 2600wh/Kg, and there is rich reserves, cheap and eco-friendly advantage, meeting the requirement of electric automobile to electrokinetic cell, is one of anode material for lithium-ion batteries with application prospect most.
But sulphur is put into practical application as positive electrode and also be there are some problem demanding prompt solutions, and first elemental sulfur is insulator, and at room temperature the conductivity of sulphur is only 5*10
-30s/cm, this causes the utilance of active material low; Secondly lithium-sulfur cell fills and in cyclic process, there is effect of shuttling back and forth, the many lithium sulfide (Li of the multiple intermediate product produced in charge and discharge process
2s
n, 2<n≤8) be soluble in electrolyte, and negative pole can be moved to through barrier film, react with cathode of lithium and cause active material to be consumed, even can form insoluble Li
2s
2or Li
2s, is deposited on the surface of Li electrode, has a strong impact on electrode performance; In addition S is worked as
8electric discharge generates Li
2during S, because the density of the two is different, along with the volumetric expansion of about 76%, easily can destroy the structural stability of porous, electrically conductive network, reduce the cyclical stability of electrode material; The more important thing is, lithium-sulfur cell is using lithium metal as negative pole, and in charge and discharge process, lithium metal easily produces dendrite, pierces through barrier film and causes short circuit to set off an explosion, there is safety problem.
And lithium sulfide can use the non-lithium material such as silicon (Si), tin (Sn) as negative pole, safer; Meanwhile, Li
2when S charging generates S, volume reduces, and conductive network keeps complete; And Li
2s is as positive electrode, and its specific capacity, also up to 1166mAh/g, is studied widely so cause.But Li
2s is also faced with some problems as positive electrode, Li
2s is also electric insulation, is also faced with the dissolving of polysulfide and effect of shuttling back and forth in circulating battery process.At present for Li
2the study on the modification of S material is modal is adopt ball grinding method by Li
2s is dispersed in conductive network, reduces Li
2s particle diameter, conductive network is modified at Li simultaneously
2s particle surface, thus improve chemical property.Although above method can improve the chemical property of lithium-sulfur cell to a certain extent, the chemical property such as specific discharge capacity and cyclicity also has a segment distance from commercialization, improvement of still needing.And lithium sulfide is easy and water reacts, directly carrying out modification to lithium sulfide needs to carry out under protective atmosphere, troublesome poeration.
Summary of the invention
The invention provides coated lithium sulfide positive electrode of a kind of three-dimensional porous graphene-supported carbon and its preparation method and application, the presoma of the coated lithium sulfate of three-dimensional porous graphene-supported carbon is prepared with wet chemical method, then the at high temperature coated lithium sulfide positive electrode of the three-dimensional porous graphene-supported carbon of fabricated in situ, using the positive pole of material direct slicing as battery, save the step of slurry preparation, coating, oven dry, decrease technological process.
A preparation method for the coated lithium sulfide positive electrode of the three-dimensional porous graphene-supported carbon of fabricated in situ, comprises the following steps:
(1) graphene oxide is dispersed in water magnetic agitation, and the solution of ultrasonic formation stable homogeneous, obtain graphene oxide solution, then add reducing agent and stirring and dissolving, obtain the solution of brown;
(2) solution of step (1) gained brown is transferred in autoclave, by airtight for autoclave be placed on 120 DEG C-200 DEG C at hydro-thermal reaction 4-12h, then lower the temperature, obtain the solution of columnar three-dimensional porous graphene;
(3) in the solution of the columnar three-dimensional porous graphene of step (2) gained, add lithium sulfate and carbon source, after stirring and dissolving, columnar three-dimensional porous graphene is soaked wherein, form the soak of columnar three-dimensional porous graphene;
(4) by the soak freeze drying of columnar three-dimensional porous graphene, presoma is obtained;
(5) step (4) gained presoma is calcined 2-12h at 800-1000 DEG C under protective atmosphere, obtain the coated lithium sulfide material of three-dimensional porous graphene-supported carbon.
In step (1), as preferably, in described graphene oxide solution, graphene oxide concentration is 1-5mg/mL, described reducing agent is one or more in thiocarbamide, citric acid, vitamin etc., in the solution of described brown, the concentration of reducing agent is 1-20mg/mL, further preferably, 1-10mg/mL.
In step (2), hydro-thermal reaction generates the temperature of columnar three-dimensional porous graphene at 120 DEG C-200 DEG C, and the hydro-thermal time is at 4-12h.As preferably, hydro-thermal reaction 8-12h at 170 DEG C-190 DEG C.Further preferably, hydro-thermal reaction 10h at 180 DEG C.
In step (3), as preferably, described lithium sulfate is Li
2sO
4or Li
2sO
4h
2o, described carbon source is one or more in the carbon compounds such as glucose, sucrose, maltose, soluble starch, polyvinylpyrrolidone, in the soak of described columnar three-dimensional porous graphene, the concentration of lithium sulfate is at 50-200mg/mL (further preferred 50-100mg/mL), and the concentration of carbon source is at 50-600mg/mL (further preferred 100-400mg/mL).
In step (4), as preferably, the freezing mode in described freeze drying is liquid nitrogen frozen or refrigerator refrigeration, and the drying mode in described freeze drying is vacuum freeze drying.
In step (5), under nitrogen or argon shield, calcining heat is 800-1000 DEG C, and calcination time is 2-12h.As preferably, under protective atmosphere, calcine 2-6h at 800-1000 DEG C.Further preferably, under protective atmosphere, 2h is calcined at 900 DEG C.
The coated lithium sulfide positive electrode of three-dimensional porous graphene-supported carbon prepared by described preparation method, in the coated lithium sulfide positive electrode of described three-dimensional porous graphene carbon, lithium sulfide content (mass percent) is at 30%-75%, and Graphene and carbon content (mass percent) are at 25%-70%.The coated lithium sulfide positive electrode of three-dimensional porous graphene-supported carbon, can directly cut into slices as anode, assembled battery.
The preparation of anode is by coated for three-dimensional porous graphene-supported carbon lithium sulfide positive electrode section, that barrier film adopts is microporous polypropylene membrane (Cellgard2300), electrolyte is for solute with two (fluoroform) sulfonamide lithium salts (LiTFSI) of 1mol/L, solvent is volume ratio is 1 of 1:1,3-dioxolanes (DOL) and glycol dimethyl ether (DME), and add the LiNO of 1.0-5.0wt%
3, negative pole uses lithium, silicon, graphite, tin etc., the assembling process of battery all be full of argon gas and water oxygen content lower than the glove box of 0.1ppm in complete.
The lithium ion battery assembled carries out constant current charge-discharge test after placing 24h, first charge-discharge voltage is 1.5V ~ 4V, charging/discharging voltage is subsequently 1.5V ~ 3V, and circulate capacity, charge-discharge performance and the multiplying power property of measuring lithium ion cell positive in 25 ± 2 DEG C of environment.
Compared with prior art, tool of the present invention has the following advantages:
The present invention adopts Graphene, lithium sulfate and carbon source to be that raw material pyroreaction generates the coated lithium sulfide positive electrode of three-dimensional porous graphene-supported carbon; with directly adopt compared with commercialization lithium sulfide; with low cost; material direct slicing is prepared into anode; save the step of slurry preparation, coating, oven dry; preparation technology is simple, is applicable to large-scale production.Three-dimensional porous Graphene provides reaction site for the reaction of lithium sulfate and carbon source, three-dimensional porous Graphene improves the electric conductivity of material as conductive network simultaneously, the structure of the coated lithium sulfide of in-situ preparation carbon can improve the conductivity of lithium sulfide electrode, the dissolving of polysulfide in electrochemical reaction process can be reduced simultaneously, suppress to shuttle back and forth effect, keep the stability of clad structure, thus improve battery capacity and cycle life.The coated lithium sulfide positive electrode of the three-dimensional porous graphene-supported carbon of fabricated in situ of the present invention is utilized to be applicable to high-energy-density energy storage device.
Accompanying drawing explanation
Fig. 1 is the process schematic of the coated lithium sulfide positive electrode of the three-dimensional porous graphene-supported carbon of embodiment 1 fabricated in situ;
Fig. 2 is the XRD collection of illustrative plates of the coated lithium sulfide positive electrode of three-dimensional porous graphene-supported carbon prepared by embodiment 1;
Fig. 3 is the SEM photo of the three-dimensional porous graphene-supported carbon of embodiment 1 fabricated in situ coated lithium sulfide positive electrode different amplification, and wherein, in Fig. 3, (a) is the SEM pattern under low power, and in Fig. 3, (b) is the SEM pattern under high power;
Fig. 4 is the cyclic voltammetry curve adopting the coated lithium sulfide positive electrode of three-dimensional porous graphene-supported carbon of embodiment 1 to prepare battery;
Fig. 5 is the cycle performance of battery under 1C adopting the coated lithium sulfide positive electrode of three-dimensional porous graphene-supported carbon of embodiment 1 to prepare.
Embodiment
Describe the present invention in detail below in conjunction with embodiment and accompanying drawing, but the present invention is also not only confined to this.
Embodiment 1
(1) graphene oxide is dispersed in magnetic agitation in 140g deionized water, and ultrasonic 1h forms the solution of stable homogeneous, in graphene oxide solution, the concentration of graphene oxide is 2mg/ml, then reducing agent thiocarbamide is added and stirring and dissolving, obtain the solution of brown, in the solution of brown, the concentration of reducing agent thiocarbamide is 1.5mg/mL;
(2) solution of above-mentioned gained brown is transferred in autoclave, by airtight for autoclave be placed on 180 DEG C at be incubated 10h, then treat that autoclave temperature is down to room temperature 25 DEG C, obtain the solution of columnar three-dimensional porous graphene;
(3) in the solution of the columnar three-dimensional porous graphene of gained, sulfuric acid monohydrate lithium and glucose is added, after stirring and dissolving, columnar three-dimensional porous graphene is soaked wherein, form the soak of columnar three-dimensional porous graphene, in the soak of columnar three-dimensional porous graphene, the concentration of sulfuric acid monohydrate lithium is at 70mg/mL, and the concentration of carbon source glucose is at 280mg/mL;
(4) by fully soak after columnar three-dimensional porous graphene liquid nitrogen frozen, then vacuum freeze drying, obtains presoma;
(5) presoma is calcined 2h at 900 DEG C under argon atmosphere, be obtained by reacting the coated lithium sulfide material of three-dimensional porous graphene-supported carbon;
(6) using the positive pole of coated for three-dimensional porous graphene-supported carbon lithium sulfide material section as battery, lithium ion battery is assembled into as battery cathode using metal lithium sheet, that barrier film adopts is microporous polypropylene membrane (Cellgard2300), electrolyte is for solute with two (fluoroform) sulfonamide lithium salts (LiTFSI) of 1mol/L, volume ratio is 1 of 1:1,3-dioxolanes (DOL) and glycol dimethyl ether (DME) are solvent, and add the LiNO of 1.0wt%
3, battery assembling process all be full of argon gas and water oxygen content lower than the glove box of 0.1ppm in complete.
The process of the preparation of the coated lithium sulfide positive electrode of fabricated in situ three-dimensional grapheme load carbon and battery thereof as shown schematically in fig. 1.
The coated lithium sulfide positive electrode of fabricated in situ three-dimensional grapheme load carbon is by x-ray photoelectron spectroscopy (X-rayphotoelectronspectroscopy) test, as shown in Figure 2, for the present embodiment prepares the XRD collection of illustrative plates of the coated lithium sulfide positive electrode of the three-dimensional porous graphene-supported carbon of fabricated in situ.According to Fig. 2, the coated lithium sulfide material of the three-dimensional porous graphene-supported carbon of fabricated in situ of fabricated in situ prepared by the present embodiment generates lithium sulfide (JCPDSCardNo.04-0664) standard phase.The SEM picture of the end product obtained is as shown in Fig. 3 a, 3b, Fig. 3 a is the pattern under product low power, as we can see from the figure, the three-dimensional porous Graphene that the Thickness Ratio of three-dimensional porous Graphene is simple increases to some extent, Fig. 3 b is the SEM pattern under sample high power, can see that on Graphene, some particles in load, this is the coated lithium sulfide of carbon, illustrates that thickening of Graphene is that the coated lithium sulfide of load carbon causes.According to thermogravimetric, can calculate the content of lithium sulfide probably 40%, Graphene and carbon content are 60%.
The lithium ion battery assembled carries out constant current charge-discharge test after placing 24h, first charge-discharge voltage is 1.5V ~ 4V, charging/discharging voltage is subsequently 1.5V ~ 3V, and circulate capacity, charge-discharge performance and the multiplying power property of measuring lithium ion cell positive in 25 ± 2 DEG C of environment.
After being assembled into lithium ion battery, carry out various electrochemical property test.Fig. 4 is cyclic voltammogram, and first time charging, be first charged to 4V, this needs to overcome potential barrier because lithium sulfide is converted in the process of polysulfide, and in process subsequently, charging/discharging voltage is 1.5V to 3V, is typical lithium-sulfur cell charging and discharging curve.In charging process, near 2.4V, there is an oxidation peak, correspond to Li
2s
2or Li
2s is oxidized to polysulfide Li
2s
nprocess, in discharge process, have two reduction peak at 2.3V and 2.0V place, corresponding sulphur is converted into the Li of long-chain respectively
2s
n(4≤n≤8) and from Li
2s
n(4≤n≤8) are reduced to the Li of short chain
2s
2or Li
2the process of S.Shown in Fig. 5 is the cycle performance figure of battery under 1C that this example implements preparation, the activation process of first circulation for being charged to 4V, under current density is 1C, the discharge capacity first of battery is 510mAh/g, after 100 circulations, discharge capacity maintains 414mAh/g, conservation rate is 81%, show good cycle performance, and coulombic efficiency remains on more than 95%.
Embodiment 2
(1) graphene oxide is dispersed in magnetic agitation in 140g deionized water, and ultrasonic 1h forms the solution of stable homogeneous, in graphene oxide solution, the concentration of graphene oxide is 3mg/ml, then reducing agent thiocarbamide is added and stirring and dissolving, obtain the solution of brown, in the solution of brown, the concentration of reducing agent thiocarbamide is 5mg/mL;
(2) solution of above-mentioned gained brown is transferred in autoclave, by airtight for autoclave be placed on 180 DEG C at be incubated 10h, then treat that autoclave temperature is down to room temperature 25 DEG C, obtain the solution of columnar three-dimensional porous graphene;
(3) in the columnar three-dimensional porous graphene and solution of gained, lithium sulfate is added and number-average molecular weight is the polyvinylpyrrolidone of 58000, and columnar three-dimensional porous graphene is soaked wherein, obtain the soak of columnar three-dimensional porous graphene, in the soak of columnar three-dimensional porous graphene, the concentration of lithium sulfate is at 50mg/mL, and the concentration of carbon source polyvinylpyrrolidone is at 200mg/mL;
(4) by the soak liquid nitrogen frozen of columnar three-dimensional porous graphene, then vacuum freeze drying, obtains presoma;
(5) presoma is calcined 2h at 900 DEG C under argon atmosphere, be obtained by reacting the coated lithium sulfide material of three-dimensional porous graphene-supported carbon;
(6) using the positive pole of coated for three-dimensional grapheme load carbon lithium sulfide positive electrode section as battery, lithium ion battery is assembled into as battery cathode using metal lithium sheet, that barrier film adopts is microporous polypropylene membrane (Cellgard2300), electrolyte be with by two for 1mol/L (fluoroform) sulfonamide lithium salts (LiTFSI) for solute, volume ratio is 1 of 1:1,3-dioxolanes (DOL) and glycol dimethyl ether (DME) are solvent, and add the LiNO of 1.0wt%
3, battery assembling process all be full of argon gas and water oxygen content lower than the glove box of 0.1ppm in complete.
The coated lithium sulfide positive electrode of fabricated in situ three-dimensional grapheme load carbon, by x-ray photoelectron spectroscopy (X-rayphotoelectronspectroscopy) test, can determine that the coated lithium sulfide material of fabricated in situ three-dimensional grapheme load carbon generates lithium sulfide.According to thermogravimetric, can calculate the content of lithium sulfide probably 35%, carbon content is 65%.
The lithium ion battery assembled carries out constant current charge-discharge test after placing 24h, first charge-discharge voltage is 1.5V ~ 4V, charging/discharging voltage is subsequently 1.5V ~ 3V, and circulate capacity, charge-discharge performance and the multiplying power property of measuring lithium ion cell positive in 25 ± 2 DEG C of environment.Battery when current density is 1C first discharge capacity be 680mAh/g, 100 times circulation after discharge capacity be 450mAh/g, functional.
Claims (10)
1. a preparation method for the coated lithium sulfide positive electrode of the three-dimensional porous graphene-supported carbon of fabricated in situ, is characterized in that, comprise the following steps:
(1) graphene oxide is dispersed in water magnetic agitation, and the solution of ultrasonic formation stable homogeneous, obtain graphene oxide solution, then add reducing agent and stirring and dissolving, obtain the solution of brown;
(2) solution of step (1) gained brown is transferred in autoclave, by airtight for autoclave be placed on 120 DEG C-200 DEG C at hydro-thermal reaction 4-12h, then lower the temperature, obtain the solution of columnar three-dimensional porous graphene;
(3) in the solution of the columnar three-dimensional porous graphene of step (2) gained, add lithium sulfate and carbon source, after stirring and dissolving, columnar three-dimensional porous graphene is soaked wherein, form the soak of columnar three-dimensional porous graphene;
(4) by the soak freeze drying of columnar three-dimensional porous graphene, presoma is obtained;
(5) step (4) gained presoma is calcined 2-12h at 800-1000 DEG C under protective atmosphere, obtain the coated lithium sulfide material of three-dimensional porous graphene-supported carbon.
2. preparation method according to claim 1, is characterized in that, in step (1), in described graphene oxide solution, graphene oxide concentration is 1-5mg/mL.
3. preparation method according to claim 1, is characterized in that, in step (1), described reducing agent is one or more in thiocarbamide, citric acid, vitamin.
4. preparation method according to claim 1, is characterized in that, in step (1), in the solution of described brown, the concentration of reducing agent is 1-20mg/mL.
5. preparation method according to claim 1, is characterized in that, in step (2), and hydro-thermal reaction 8-12h at 170 DEG C-190 DEG C.
6. preparation method according to claim 1, is characterized in that, in step (3), described carbon source is one or more in glucose, sucrose, maltose, soluble starch, polyvinylpyrrolidone.
7. preparation method according to claim 1, is characterized in that, in step (3), in the soak of described columnar three-dimensional porous graphene, the concentration of lithium sulfate is at 50-200mg/mL, and the concentration of carbon source is at 50-600mg/mL.
8. the coated lithium sulfide positive electrode of three-dimensional porous graphene-supported carbon prepared by preparation method according to claims 1 to 7.
9. the coated lithium sulfide positive electrode of three-dimensional porous graphene-supported carbon according to claim 8, it is characterized in that, in the coated lithium sulfide positive electrode of described three-dimensional porous graphene carbon, lithium sulfide mass percentage is at 30%-75%, and Graphene and carbon mass percentage are at 25%-70%.
10. the coated lithium sulfide positive electrode of three-dimensional porous graphene-supported carbon is according to claim 8 or claim 9 as the application in anode.
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| CN105869903A (en) * | 2016-05-25 | 2016-08-17 | 全球能源互联网研究院 | Preparation method of graphene |
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| CN111628166A (en) * | 2020-06-04 | 2020-09-04 | 合肥工业大学 | Three-dimensional lithium sulfide electrode for lithium-sulfur battery and preparation method thereof |
| CN112909248A (en) * | 2021-02-20 | 2021-06-04 | 电子科技大学 | Li based on 3D printing2S positive electrode material and preparation method thereof |
| CN114300655A (en) * | 2021-12-31 | 2022-04-08 | 杭州电子科技大学 | Lithium sulfide electrode based on titanium oxide nanotube and preparation method thereof |
| CN114497499A (en) * | 2022-01-26 | 2022-05-13 | 中汽创智科技有限公司 | Lithium sulfide/carbon composite material with multilevel structure and preparation method and application thereof |
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| CN108584927A (en) * | 2018-05-24 | 2018-09-28 | 浙江农业商贸职业学院 | A kind of preparation method of porous graphene powder for automotive alloys material |
| CN110137462A (en) * | 2019-05-10 | 2019-08-16 | 浙江大学 | Preparation method for aluminium/lithium sulphide battery vulcanization lithium/carbon composite material |
| CN110350175A (en) * | 2019-07-11 | 2019-10-18 | 安徽师范大学 | A kind of composite material of the graphene-supported sulphur of porous carbon@, preparation method and applications |
| CN111628166A (en) * | 2020-06-04 | 2020-09-04 | 合肥工业大学 | Three-dimensional lithium sulfide electrode for lithium-sulfur battery and preparation method thereof |
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