CN103715402A - Lithium sulphur battery anode material based on volcanic rock as well as preparation and application method of lithium sulphur battery anode material - Google Patents
Lithium sulphur battery anode material based on volcanic rock as well as preparation and application method of lithium sulphur battery anode material Download PDFInfo
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Abstract
The invention discloses a lithium sulphur battery anode material based on volcanic rock as well as a preparation and an application method of the lithium sulphur battery anode material. According to the anode material disclosed by the invention, the volcanic rock powder is used as a skeleton, elemental sulfur is filled in volcanic rock holes, and a sulphur-loading composite material is obtained and is coated with a conductive substance; as the volcanic rock reduces the dissolution of polysulfide, the volume expansion of the sulphur in a charge-discharge process is restricted, the conductivity of the material is greatly enhanced through the coating of the conductive substance, and the capacity of a lithium sulphur battery is increased. The lithium sulphur battery anode material as well as the preparation and the application method thereof, which are disclosed by the invention, have the advantages that the preparation technology is simple, the volcanic rock belongs to a natural environment-friendly material, the cost is low, and the lithium sulphur battery industrialization is easily realized; meanwhile, the industrial transformation and upgrade of nonmetallic minerals are promoted by introduction of the volcanic rock.
Description
Technical field
The invention belongs to new energy materials field, particularly relate to a kind of lithium sulfur battery anode material and methods for making and using same thereof based on volcanic rock.
Background technology
Along with the continuous aggravation of the day by day serious and energy crisis of environmental pollution, high-energy-density, the exploitation of renewable energy system cheaply become the emphasis that people study gradually.Because elemental sulfur has that height ratio capacity, price are low, environmental friendliness and the feature such as density is light, be considered to a kind of good anode material of lithium battery.Lithium-sulfur cell is usingd elemental sulfur as anode reactant matter, and lithium metal is as negative pole, and theoretical energy density can reach 2600Wh/kg.Compare with traditional lithium ion battery, lithium-sulfur cell can be realized its energy density of 3 to 5 times, thereby becomes the focus of the current concern of people.
However, still there is the problem of following three aspects in lithium-sulfur cell: many lithium sulfides that (1) lithium-sulfur cell charge and discharge process produces are soluble in organic electrolyte, the active material of electrode is reduced gradually, and due to the principle of shuttling back and forth, the many lithium sulfides that dissolve can reach on the negative pole lithium sheet of battery through barrier film, and the product electric conductivity such as the lithium sulfide of generation are poor and do not dissolve, thereby cause the corrosion of battery cathode and the increase of the internal resistance of cell, the cycle performance variation that causes battery, capacity is progressively decayed.(2) poorly conductive of sulphur, the high rate capability that is unfavorable for battery, just very the Li/S battery of 100% sulphur can not discharge and recharge when room temperature, this is because ionic conductivity and the electron conduction of sulphur are all very low, cause the problems such as the chemical property of sulphur in electrode is not good and utilance is low, generally by sulphur and carbon or the compound problem that can solve its conduction difference of other electric conducting materials.(3) sulphur is in charge and discharge process, and the expansion of volume is dwindled very large, likely causes battery to damage, because in cyclic process, in lithium-sulfur cell, the volume deformation of sulfur electrode, up to 22%, may make the inner micro-crack that produces of sulfur electrode.The existence of this micro-crack and insulation phase Li
2s has destroyed the globality of electrode in the generation of cracks, finally aggravate the capacity attenuation of lithium-sulfur cell.
At present, in order to overcome the problem of lithium-sulfur cell capacity attenuation, people mainly improve from following three aspects: (1) suppresses the too much dissolving of polysulfide, mainly by the structure of design conductive phase, make it have the ability of absorption polysulfide, or improve the electrolyte system of battery; (2) add the compound object that improves conductivity that reaches of one or more electronic conductors and sulphur; (3) protection of cathode of lithium.
Summary of the invention
One of object of the present invention is to provide a kind of positive electrode, and it successfully adopts volcanic rock to carry sulfur materials to prepare lithium-sulphur cell positive electrode, the methods for making and using same of this material is also provided first.This material can reduce the dissolving of polysulfide and suppress the volumetric expansion of sulphur in charge and discharge process, improves the cycle performance of lithium-sulfur cell, and carries positive pole prepared by sulfur materials with general artificial synthetic porous and compare, and performance is more advantageous.In addition, volcanic rock cheap, amount is large, and owing to being natural products, without synthetic, obtain conveniently.
Two of object of the present invention is also to provide a kind of positive electrode and application process thereof, to carry coated with conductive material on sulfur materials basis at volcanic rock, strengthened the conductivity of material, improved the capacity of lithium-sulfur cell, the cathode performance of preparing than artificial synthesizing porous year sulfur materials of general coated with conductive material goes out well a lot.
A lithium sulfur battery anode material based on volcanic rock, is to take volcanic rock dusty material as skeleton, and elemental sulfur is injected to year sulphur composite material that volcano petrosal foramen obtains.Preferably the mass ratio of elemental sulfur and volcanic rock is no more than 1.
Volcanic rock powder diameter scope is less than 200 μ m; Preferred 150nm-800nm.
The described lithium sulfur battery anode material based on volcanic rock, can also carry out conductive materials to a described year sulphur composite material again and be coated.
Described conductive materials comprises metallic element or conducting polymer.
Metallic element comprises: silver, copper, gold, aluminium, molybdenum, tungsten, zinc, nickel, iron, platinum or tin; Conducting polymer comprises: polyacetylene, polythiophene, polypyrrole, polyaniline, polyhenylene, polyphenylene ethylene, poly-two alkynes.Coated conductive materials thickness is 10nm-10 μ m; Preferred 50-200nm.
A preparation method for lithium sulfur battery anode material based on volcanic rock, comprises the following steps:
1) preliminary treatment volcanic rock: the volcanic rock powder that particle size range is less than to 200 μ m cleans with deionized water, then to its sonic oscillation 1-2h; Then put 85-100 ℃ of dry 10-24h in baking oven into; Volcanic rock powder is added to pickling processes 1-2h in 1-10mol/L HCl solution, clean; Volcanic rock powder is incubated to 1-2h at 100-150 ℃ under vacuum condition, under vacuum condition, is cooled to room temperature, obtain the volcanic rock dusty material after purifying;
2) note sulphur: adopt a kind of in vacuum heat method, protective atmosphere heat treating process, chemical method, exchange of solvent method to note sulphur to volcanic rock powder.
Step 2) in, the step of vacuum heat method is as follows: under a, vacuum state, melting elemental sulfur injects the hole of volcanic rock powder; B, then continue under vacuum state heating by the unnecessary sulphur distillation in volcanic rock surface, be cooled to room temperature, dry.
In step a, the vacuum ranges of vacuum fusion note sulphur technique is at 0.1-100Pa, and the reaction temperature that elemental sulfur liquefies is in a vacuum at 40-100 ℃, reaction time 1-3h; In step b, vacuum ranges is at 0.1-100Pa, and the reaction temperature of gasification is at 60 ℃-120 ℃, reaction time 10-30min.
The preparation method of the described lithium sulfur battery anode material based on volcanic rock, continues elemental sulfur to inject year sulphur composite material coated with conductive material that volcano petrosal foramen obtains, and coated conductive materials thickness is 10nm-10 μ m; Preferred 50-200nm.
The present invention compared with prior art, has following beneficial effect:
1, the present invention is applied to lithium-sulfur cell by this nonmetallic mineral material of volcanic rock and even whole field of batteries has no relevant report in document, Domestic News at home and abroad.The present invention is by adopting the volcanic rock powder of natural cheapness as the preparation-obtained lithium sulfur battery anode material of framework material, can effectively suppress the volumetric expansion of sulphur in charge and discharge process and reduce the dissolving of polysulfide.And volcanic rock is to contain abundant sodium, magnesium, aluminium, silicon, calcium, manganese, iron, phosphorus, nickel, the mineral matter of the labyrinth form of tens kinds of elements such as cobalt, use it for the positive pole of preparing lithium-sulfur cell, there is following unexpected technique effect, 1) the pleasantly surprised discovery the present invention of inventor adopts performance that volcanic rock carries sulphur positive electrode to be much better than porous charcoal and carries positive pole prepared by sulfur materials, 2) the present invention adopts the volcanic rock performance of carrying sulphur positive electrode and the porous charcoal that has been coated conductive materials to carry cathode performance prepared by sulfur materials to remain basically stable, this is that those skilled in the art do not expect and obtain, 3) porous charcoal that the performance that the volcanic rock that has been coated conductive materials carries sulphur positive electrode is also much better than coated with conductive material is carried positive pole prepared by sulfur materials.Referring to data of the present invention: the volcanic rock that adopts the present invention to prepare carries sulphur composite positive pole and cathode of lithium is assembled into button cell (embodiment 1), under room temperature condition when 0.2C constant current charge-discharge, first discharge specific capacity reaches 1050.4mAh/g, circulating, Capacitance reserve is at 770.5mAh/g after 200 times, and capability retention reaches 73.3%.Carry positive pole (three data of comparative example 1 prepared by sulfur materials with general artificial synthetic porous charcoal, 955.3,647.4,67.8%) compare, it is superior many that performance is wanted, carry positive pole (three data of comparative example 2 prepared by sulfur materials with the porous charcoal that has been coated conductive materials, 1055.1,791.6,75%) compare, remain basically stable.And being coated the volcanic rock of conductive materials, the present invention carries sulfur materials, further strengthened the conductivity of material, improved the capacity of lithium-sulfur cell, the embodiment of the present invention 2,3,4 has all been coated electric conducting material, and the porous charcoal that its performance data is obviously better than documents 2 coated with conductive materials is carried sulfur materials.
2, abundant raw material and cheap.Common porous carbon materials price is about 5000 yuan/ton in the market, and volcanic rock is as a kind of natural nonmetallic mineral material, has removed the processing preparation technology of other materials complexity from.And the market price of the former stone of volcanic rock is about 600 yuan/ton, the price being processed into after powder is only also 1500 yuan/ton of left and right, as the framework material in lithium-sulphur cell positive electrode, has very large price advantage.
3, preparation technology is simple.
In sum, volcanic rock is a kind of in nonmetallic mineral material, low-cost natural green environment-friendly materials, it is applied to lithium-sulfur cell field as carrying sulphur complex, can reduce the dissolving of polysulfide and suppress the volumetric expansion of sulphur in charge and discharge process, improve the cycle performance of lithium-sulfur cell.The present invention is compound by volcanic rock and sulphur are carried out, and has prepared the positive electrode that can be used for lithium-sulfur cell, and the lithium-sulfur cell capacity that assembles is high, good cycle.And adopt the coated means of conductive materials to improve the conductivity of positive electrode, thereby promoted active material utilization, effectively suppressed the problem of lithium-sulfur cell capacity attenuation, be conducive to the industrialization of lithium-sulfur cell.At present, have no volcanic rock both at home and abroad as the relevant report of battery electrode material.
Accompanying drawing explanation
Fig. 1 is the structural representation that the coated volcanic rock of conductive materials of the present invention carries sulfur materials, 1 volcanic rock dusty material in figure, and in figure, 2 for injecting the sulphur of volcanic rock hole, and in figure, 3 is the coated controlled conductive materials of thickness;
Fig. 2 is 200 the discharge capacity curve charts of lithium-sulfur cell that obtain according to embodiment 1;
Fig. 3 is the SEM figure that the coated volcanic rock of nickel that obtains by embodiment 2 carries sulfur materials;
Fig. 4 is the thermogravimetric curve figure that the coated volcanic rock of nickel that obtains by embodiment 2 carries sulfur materials;
Fig. 5 is the lithium-sulfur cell first charge-discharge platform figure obtaining by embodiment 2;
Fig. 6 is 200 the discharge capacity curve charts of lithium-sulfur cell that obtain by embodiment 2;
Fig. 7 is the lithium-sulfur cell multiplying power figure obtaining by embodiment 3;
Fig. 8 is 200 the discharge capacity curve charts of lithium-sulfur cell that obtain by embodiment 3;
Fig. 9 is the lithium-sulfur cell multiplying power figure obtaining by embodiment 3;
Figure 10 is 200 the discharge capacity curve charts of lithium-sulfur cell that obtain by embodiment 4;
Figure 11 is the lithium-sulfur cell multiplying power figure obtaining by embodiment 4;
Figure 12 is 200 the discharge capacity curve charts of lithium-sulfur cell that obtain by comparative example 1;
Figure 13 is 200 the discharge capacity curve charts of lithium-sulfur cell that obtain by comparative example 2.
Embodiment
The following examples are to further illustrate of the present invention, but do not limit the scope of the invention.
In following examples and comparative example, elemental sulfur used is sublimed sulfur, granularity is 10nm-1 μ m, sulfenyl composite reactive material, conductive agent and binding agent mass ratio 7:2:1 in pole piece preparation, wherein conductive agent is acetylene carbon black, binding agent is Kynoar, solvent is 1-METHYLPYRROLIDONE, and collector is aluminium foil.
Preliminary treatment volcanic rock powder: choose particle diameter and be less than 5 μ m volcanic rock powder, clean with deionized water, then the volcanic rock after cleaning is carried out to sonic oscillation 1h, then 85 ℃ of dry 24h in baking oven.Volcanic rock is added to pickling processes 2h in 10mol/L HCl solution, then activate in advance, volcanic rock powder is incubated to 2h at 100 ℃ under vacuum condition, under vacuum condition, be cooled to room temperature, obtain the volcanic rock dusty material after purifying.
Volcanic rock dusty material after above-mentioned preliminary treatment is evenly mixed with elemental sulfur 1:1, be positioned in quartz boat, under the condition that is 100Pa in vacuum degree, with 2 ℃/min, be heated to 100 ℃, constant temperature 2h, continue again biased sample to be heated to 120 ℃ with the heating rate of 2 ℃/min, constant temperature 0.5h, keeps this vacuum condition and with the rate of temperature fall of 2 ℃/min, is down to room temperature again.Sample is further ground, dry, make volcanic rock and carry sulfur materials.
Select the volcanic rock obtaining in embodiment 1 to carry sulfur materials, carry out the preparation that the coated volcanic rock of nickel carries sulfur materials: volcanic rock is carried to sulfur materials and carry out preliminary treatment, evenly coated to guarantee clad metal, there is good adhesive force.
1. oil removing: get 5g volcanic rock and carry sulfur materials in 200ml ethanolic solution, add the HCl of 100ml 37%, sonic oscillation 20min, 30 ℃ of temperature, are neutral by washed with de-ionized water to pH, are filtered dry.
2. sensitization: above-mentioned volcanic rock is carried to sulfur materials at 10g/L SnCl
22H
2in O+40g/L HCL solution, carry out sensitization and process 30min, washed with de-ionized water, is filtered dry.
3. activation: volcanic rock after sensitization is carried to sulfur materials at 0.5g/L PdCl
2activation processing 30min in+0.25mL HCl solution, washed with de-ionized water, is filtered dry.
4. reduction: the volcanic rock after activation is carried to sulfur materials soak 0.5-2min in 3% sodium hypophosphite solution, washed with de-ionized water, is filtered dry.
5. electroless plating nickel:
Chemical nickel-plating plating solution main component is:
25g/L NiSO
46H
2o, 20g/L NaH
2pO
2h
2o, 25g/L NaC
2h
3o
2with 15g/L Na
3c
6h
7o
72H
2o
Surfactant is appropriate.
PH reconciles to 8.2 with ammoniacal liquor.
Volcanic rock after reduction is carried to sulfur materials and put into above-mentioned chemical nickel-plating plating solution, 86 ℃ of chemical plating temperature, time 60s, then pass through filtration drying, obtain the coated volcanic rock of nickel and carry sulfur materials.
In sensitization, activation, nickel process, adopt sonic oscillation always.
Under these conditions, make the coated volcanic rock of nickel that plated thickness is about 160nm and carry sulfur materials.
Fig. 3 is that the nickel that embodiment 2 makes is coated the SEM figure that volcanic rock carries sulfur materials.
The technical process of preliminary treatment volcanic rock powder is identical with embodiment 1.
Volcanic rock dusty material after preliminary treatment is evenly mixed with elemental sulfur 1:1, be positioned in quartz boat, in the tube furnace that passes into Ar gas, be heated to 155 ℃; constant temperature 12h; continuation is heated to 160 ℃ by biased sample, and constant temperature 6h keeps this protective atmosphere condition and is cooled to room temperature.Sample is further ground, dry, make volcanic rock and carry sulfur materials.
Copper clad volcanic rock carries the preparation of sulfur materials: except reduction and chemical plating employing solution composition and technique below, by the step identical with embodiment 2, prepare.
Reduction: the volcanic rock after activation is carried to sulfur materials soak 0.5-2min in 10% formalin, washed with de-ionized water, is filtered dry.
Electroless copper is coated:
Electroless copper plating solution main component is:
25g/L CuSO
45H
2o, 40g/L NaKC
4h
4o
24H
2o, 10g/L Na
2cO
3with 10ml/L HCHO (37%).
Surfactant is appropriate.
PH reconciles to 11.8 with ammoniacal liquor.
Volcanic rock after reduction is carried to sulfur materials and put into above-mentioned electroless copper plating solution, 25 ℃ of chemical plating temperature, time 60s, then pass through filtration drying, the volcanic rock that obtains copper clad carries sulfur materials.
In sensitization, activation, electroless copper process, adopt sonic oscillation always.
Under these conditions, make the copper clad volcanic rock that plated thickness is about 150nm and carry sulfur materials.
Embodiment 4
The technical process of preliminary treatment volcanic rock powder is identical with embodiment 1.
Get 2g Na
2s, in the beaker of 100ml, adds a certain amount of distilled water to form Na
2s solution.Then 3g sublimed sulfur is joined to Na
2in S solution, then with magnetic stirring apparatus, at room temperature stir 2h.By the dissolving of sulphur, solution changes into orangely from light yellow, obtains sodium polysulfide solution.
Volcanic rock material after the preliminary treatment of 1.5g is joined in the NMP of 1L, and 50 ℃ of sonic oscillation 5h, add appropriate cetyl trimethyl bromine ammonium to increase the surface activity of volcanic rock, form a stable volcanic rock solution.Then, above-mentioned synthetic sodium polysulfide solution is mixed to join in above-mentioned volcanic rock solution, sonic oscillation 2h, is added drop-wise to mixed solution in the HCOOH solution of 2mol/L, the volcanic rock precipitation after being vulcanized.To cross filter cake and respectively clean 3 times with acetone and distilled water, deposit sample will be placed in to 50 ℃ of constant temperature 72h of drying box, and obtain volcanic rock and carry sulfur materials.
The preparation that the coated volcanic rock of polypyrrole carries sulfur materials:
The 4.0g volcanic rock that takes above-mentioned preparation carries sulfur materials, adds in 200ml ethanolic solution, adds appropriate softex kw, and magnetic agitation 6h, to strengthen the surface activity of volcanic rock.
0.5g polypyrrole is joined in above-mentioned solution, and magnetic agitation 12h, by solution suction filtration, respectively cleans 3 times with ethanol and deionized water.
Put into 60 ℃ of constant temperature 24h of drying box, the volcanic rock that obtains polymer overmold carries sulfur materials.
Comparative example 1
Preliminary treatment porous carbon dusty material.Choose particle diameter and be less than 5 μ m porous carbon powder, adopt the pretreating process in embodiment 1 to process porous carbon materials.
Porous carbon dusty material after above-mentioned preliminary treatment is evenly mixed with elemental sulfur 1:1, be positioned in quartz boat, under the condition that is 100Pa in vacuum degree, with 2 ℃/min, be heated to 100 ℃, constant temperature 2h, continue again biased sample to be heated to 120 ℃ with the heating rate of 2 ℃/min, constant temperature 0.5h, keeps this vacuum condition and with the rate of temperature fall of 2 ℃/min, is down to room temperature again.Sample is further ground, dry, make porous carbon supported sulfur materials.
Comparative example 2
Preliminary treatment porous carbon dusty material.Choose particle diameter and be less than 5 μ m porous carbon powder, adopt the pretreating process in embodiment 1 to process porous carbon materials.
Porous carbon dusty material after above-mentioned preliminary treatment is evenly mixed with elemental sulfur 1:1, be positioned in quartz boat, under the condition that is 100Pa in vacuum degree, with 2 ℃/min, be heated to 100 ℃, constant temperature 2h, continue again biased sample to be heated to 120 ℃ with the heating rate of 2 ℃/min, constant temperature 0.5h, keeps this vacuum condition and with the rate of temperature fall of 2 ℃/min, is down to room temperature again.Sample is further ground, dry, make porous carbon supported sulfur materials.
The preparation of the porous carbon supported sulfur materials of copper clad.The preparation of the porous carbon supported sulfur materials of copper clad is identical with the technical process that copper clad volcanic rock in above-described embodiment 3 carries sulfur materials.
By embodiment 1,2,3,4 and comparative example 1,2 prepared composite positive poles, conductive black, Kynoar (PVDF) evenly mix according to the mass ratio of 70:20:10, add appropriate NMP, are then coated in aluminum foil current collector, after dry, compressing tablet obtains a kind of lithium-sulphur cell positive electrode sheet, after weighing, put into the glove box of argon gas atmosphere and assemble button lithium-sulfur cell, lithium sheet is made negative pole, the LiTFSI/DOL:DEM that electrolyte is 1mol/L (1:1 volume ratio, DOL:1,3-dioxolanes; DME: glycol dimethyl ether), barrier film adopts Celgard2400, and housing adopts CR2032.After the battery assembling is placed to 24h, carry out electrochemical property test, probe temperature is room temperature, and test multiplying power is 0.2C, and test voltage scope is 1.0--3.0V.The specific capacity that the calculating of specific capacity of the present invention is is benchmark by the content of sulphur in positive electrode, test result is as shown in table 1 below.
Table 1
Claims (9)
1. the lithium sulfur battery anode material based on volcanic rock, is characterized in that, is to take volcanic rock dusty material as skeleton, and elemental sulfur is injected to year sulphur composite material that volcano petrosal foramen obtains.
2. the lithium sulfur battery anode material based on volcanic rock according to claim 1, is characterized in that, volcanic rock powder diameter scope is less than 200 μ m.
3. the lithium sulfur battery anode material based on volcanic rock according to claim 1, is characterized in that, then carries a sulphur composite material to carry out conductive materials coated described; Described conductive materials comprises metallic element or conducting polymer.
4. the lithium sulfur battery anode material based on volcanic rock according to claim 3, is characterized in that, metallic element comprises: silver, copper, gold, aluminium, molybdenum, tungsten, zinc, nickel, iron, platinum or tin; Conducting polymer comprises: polyacetylene, polythiophene, polypyrrole, polyaniline, polyhenylene, polyphenylene ethylene, poly-two alkynes.
5. according to the lithium sulfur battery anode material based on volcanic rock described in claim 3 or 4, it is characterized in that, coated conductive materials thickness is 10nm-10 μ m.
6. a preparation method for the lithium sulfur battery anode material based on volcanic rock, is characterized in that, comprises the following steps:
1) preliminary treatment volcanic rock: the volcanic rock powder that particle size range is less than to 200 μ m cleans with deionized water, then to its sonic oscillation 1-2h; Then put 85-100 ℃ of dry 10-24h in baking oven into; Volcanic rock powder is added to pickling processes 1-2h in 1-10mol/L HCl solution, clean; Volcanic rock powder is incubated to 1-2h at 100-150 ℃ under vacuum condition, under vacuum condition, is cooled to room temperature, obtain the volcanic rock dusty material after purifying;
2) note sulphur: adopt a kind of in vacuum heat method, protective atmosphere heat treating process, chemical method, exchange of solvent method to note sulphur to volcanic rock powder.
7. the preparation method of the lithium sulfur battery anode material based on volcanic rock according to claim 6, is characterized in that step 2) in the step of vacuum heat method as follows: under a, vacuum state, melting elemental sulfur injects the hole of volcanic rock powder; B, then continue under vacuum state heating by the unnecessary sulphur distillation in volcanic rock surface, be cooled to room temperature, dry.
8. the preparation method of the lithium sulfur battery anode material based on volcanic rock according to claim 7, it is characterized in that, in step a, the vacuum ranges of vacuum fusion note sulphur technique is at 0.1-100Pa, the reaction temperature that elemental sulfur liquefies is in a vacuum at 40-100 ℃, reaction time 1-3h; In step b, vacuum ranges is at 0.1-100Pa, and the reaction temperature of gasification is at 60 ℃-120 ℃, reaction time 10-30min.
9. the application process of the lithium sulfur battery anode material based on sepiolite described in claim 1-5 any one, is characterized in that, described material is for the preparation of the positive pole of lithium-sulfur cell.
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Cited By (6)
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| CN103985913A (en) * | 2014-05-16 | 2014-08-13 | 宋大余 | Process for manufacturing lithium sulfur battery |
| CN105304908A (en) * | 2015-10-16 | 2016-02-03 | 广东烛光新能源科技有限公司 | Preparation method of sulfur-containing electrode material |
| CN106920972A (en) * | 2017-04-11 | 2017-07-04 | 大连理工大学 | The preparation method and microbiological fuel cell of the novel composite anode of a kind of N doping charcoal based on sludge and porous volcanic rock |
| CN107694533A (en) * | 2017-08-03 | 2018-02-16 | 天津大学 | A kind of polypyrrole load volcanic ash compound adsorbent and preparation method and application |
| CN108539125A (en) * | 2018-04-20 | 2018-09-14 | 桑顿新能源科技有限公司 | A kind of high-energy density lithium sulphur power battery preparation method and battery |
| CN113381002A (en) * | 2014-10-14 | 2021-09-10 | 新罗纳米技术有限公司 | Nanocomposite battery electrode particles with varying properties |
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| CN105304908B (en) * | 2015-10-16 | 2018-07-03 | 广东烛光新能源科技有限公司 | A kind of preparation method of sulfur-bearing electrode material |
| CN106920972A (en) * | 2017-04-11 | 2017-07-04 | 大连理工大学 | The preparation method and microbiological fuel cell of the novel composite anode of a kind of N doping charcoal based on sludge and porous volcanic rock |
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| CN106920972B (en) * | 2017-04-11 | 2019-04-16 | 大连理工大学 | The preparation method and microbiological fuel cell of the novel composite anode of a kind of N doping charcoal based on sludge and porous volcanic rock |
| US10991967B2 (en) | 2017-04-11 | 2021-04-27 | Dalian University Of Technology | Preparation of a new type of composite anode and microbial fuel cell based on nitrogen doped biological carbon and porous volcanic rocks |
| CN107694533A (en) * | 2017-08-03 | 2018-02-16 | 天津大学 | A kind of polypyrrole load volcanic ash compound adsorbent and preparation method and application |
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