CN102751492A - Preparation method of cathode composite material of porous framework MIL-101(Cr)@S lithium sulfur battery - Google Patents
Preparation method of cathode composite material of porous framework MIL-101(Cr)@S lithium sulfur battery Download PDFInfo
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Abstract
The invention discloses a preparation method of a metal organic framework MIL-101(Cr)@S composite material which is a cathode material of a lithium sulfur battery. The preparation method comprises the following step of utilizing a fusion dispersion method to uniformly load sulfur on a three-dimensional pore of a porous crystal MIL-101(Cr) to form the MIL-101(Cr)@S composite material. A metal organic framework crystal material in the composite material has a three-dimensional framework structure with super-high specific surface area, pore volume and regular middle-micro double pores, so as to firmly adsorb a sulfur component in the three-dimensional framework in a nano manner. Therefore, the dual effect of dispersing sulfur grains and fixing the sulfur grains is achieved. An electrochemical performance test shows that the MIL-101(Cr)@S composite material prepared by the method can keep good charge-discharge reversibility under different charge-discharge densities; and the discharge specific capacities of circulating for 100 times and 120 times under the multiplying powers of 0.1 C and 0.8 C are respectively kept at 685 mAh/g and 387 mAh/g. The preparation method disclosed by the invention has the advantages that the process is simple, the operation is convenient, the performance of the material is excellent, and on the like; and the preparation method is applicable to large-scale industrial production.
Description
Technical field
The invention belongs to the materials chemistry field; Relate to the porous material is skeleton; Process through fusion-diffusion-absorption is fixed on the sulphur component in the duct of porous material with nano particle, is specifically related to the preparation method of a kind of novel porous skeleton MIL-101 (Cr) S anode composite material of lithium sulfur battery.
Background technology
Lithium-sulfur cell is to adopt elemental sulfur (or sulfur-containing compound) for anodal, and lithium metal is a negative pole, realizes one type of lithium secondary battery that chemical energy and electric energy transform each other through the chemical reaction between sulphur and the lithium.Compare with lithium rechargeable battery; Lithium-sulfur cell has very high theoretical capacity, reaches as high as 2600 Wh/kg, is a kind of high-energy-density, environmental friendliness and secondary cell cheap and easy to get; Therefore be considered to one of main representative of following electrokinetic cell application, and have the scale using value.
Yet; Be subject to the poorly conductive of sulphur and discharging product lithium sulfide thereof; And the intermediate product of formed a series of many lithium sulfides is soluble in characteristics such as electrolyte in charge and discharge process; Lithium-sulfur cell still exists the anodal utilance of sulphur than shortcomings such as low and cycle performance differences, becomes the maximum bottleneck that hinders the lithium-sulfur cell practical application.If can sulphur be scattered among a kind of porous material with small granularity form equably, can effectively improve the utilance of sulphur on the one hand; On the other hand, utilize the surface adsorption effect of porous material can effectively reduce sulphur and the loss of the many lithium sulfides of serial discharging product on positive plate thereof again.Therefore, with sulphur and the compound lithium sulphur positive electrode that can prepare high power capacity and cycle performance excellence of porous material.
At present; People adopt materials such as mesoporous carbon material or Graphene to coat the positive electrode that sulphur prepares lithium-sulfur cell more; Purpose is to improve the conductivity of sulphur, simultaneously sulphur component and electrolyte isolation is reduced the cycle performance of the loss of active component with the raising lithium-sulfur cell as far as possible.But the compound of this type of raw material of wood-charcoal material and sulphur can not well be dispersed in material surface with active component sulphur; Simultaneously, the aperture of mesoporous carbon material can not form stronger active force with the sulphur component usually greater than 2nm, therefore can not effectively stop the loss of sulphur component.
MIL-101 (Cr) mainly is through Cr
3+Ion and terephthalic acids coordination and a kind of metallic organic framework of forming (is called for short: MOFs) material.MIL-101 (Cr) has specific area (5900 m of superelevation
2/ g) and pore volume (2.3 cm
3/ g), for material provides huge surface energy, adsorption capacity is big.Simultaneously, MIL-101 (Cr) has the skeleton structure of aperture and big cage: wherein window aperture is respectively 12 and 14.5*16, belongs to pore size, can form stronger absorption affinity to small molecule component (molecular diameter is less than 12); And be respectively 29 and 34 by the cage structure that micropore is formed, and belong to mesoporous yardstick, can a large amount of spaces be provided and then improve its adsorption capacity for material.Compare with mesoporous carbon material; MIL-101 not only has higher specific area and pore volume; Can improve adsorption capacity to sulphur; And in the skeleton structure of little diplopore can form stronger active force with sulphur simple substance and sulphion, and then help improving the discharging and recharging of material than high power capacity and cycle performance.
Summary of the invention
The objective of the invention is to coat the sulphur content defectives such as inequality and cycle performance difference of loosing to existing mesoporous carbon material and Graphene, provide a kind of be adsorbed as main active force sulphur is dispersed in the preparation method of little diplopore metallic organic framework MIL-101 (Cr) crystal.The present invention utilizes fusion-diffusion-processes such as absorption, and sulphur is loaded on MIL-101 (Cr), prepares a kind of novel composite material MOFS.
The object of the invention is realized through following technical scheme:
(1) MIL-101 (Cr) metal-organic framework materials is synthetic:
Cr (NO with 2.0-2.4 g
3)
39H
2The terephthalic acids H of O and 0.833-0.996 g
2BDC is dissolved in the 30-50mL deionized water, adds the HF of 0.26-0.30 mL again, fully after the dissolving solution is moved in the polytetrafluoroethylene retort of 50-100 mL capacity, again retort is placed stainless steel outer sleeve and sealing; Retort is put into the temperature programming stove carry out hydro-thermal reaction, heating schedule is: with 5-10 oC/min solution is heated to 210-220 oC from room temperature, and keeps 8-10 h, with the rate of temperature fall of 0.4-0.6 oC/min solution is reduced to room temperature more afterwards; After treating that solution is cooled to room temperature, with crystal wash successively, dimethyl formamide (DMF) is washed and to wash the back centrifugal for ethanol, filters, drying makes MIL-101 (Cr) metal-organic framework materials.
(2) preparation of metallic organic framework MIL-101 (Cr) S composite material:
With part by weight is sulphur and MIL-101 (Cr) ball mill mixing of (1.6-3.2) S/1.0MIL-101 (Cr), then the powder behind the ball milling is put into the temperature programming stove and heat-treats, and finally obtains MIL-101 (Cr) S composite material.
In the step of the present invention (2), the weight ratio of said sulphur and MIL-101 (Cr) is: 1.6-3.2/1.0.
In the step of the present invention (2), said ball milling condition is: rotating speed is 250-400 commentaries on classics/min; The ball milling time is 2-6 hour.
In the step of the present invention (2), the process of said temperature programming may further comprise the steps:
(1) temperature-rise period: rise to 150-200 oC from room temperature with the speed of the 0.3-1.0 oC/min powder after with ball milling;
(2) thermostatic process: the mixture of MIL-101 (Cr) and sulphur is kept 1-3 h at 150-200 oC;
(3) temperature-fall period: the speed with 5-10 oC/min is reduced to room temperature with precursor solution from 150-200 oC.
The present invention compared with prior art has following beneficial effect:
(1) the present invention active component sulphur is carried on bigger serface, high pore volume and have in MIL-101 (Cr) material of little two kinds of pore structures; Can effectively improve the adhesive force of sulphur component and carrier; And then play the effect of fixing sulfur and product sulphion thereof, promote the cycle performance of lithium-sulfur cell.
(2) the present invention is carried on MIL-101 (Cr) porous material through fusion-diffusion-suction type with sulphur and forms MIL-101 (Cr) S composite material, and the sulphur component is spread in the skeleton of MIL-101 (Cr) with the nanometer small particles form equably.
(3) preparation method of the present invention is simple to operation, is fit to large-scale industrial production.
Description of drawings
Fig. 1 is the TGA curve of the embodiment of the invention one MIL-101 (Cr) S-1 composite material and bright sulfur particle;
Fig. 2 is the SEM photo of the embodiment of the invention one MIL-101 (Cr) S-1 composite material;
Fig. 3 is the N of the embodiment of the invention one MIL-101 (Cr) S-1 composite material
2Absorption/desorption isotherm;
Fig. 4 is the rate charge-discharge curve chart of the embodiment of the invention one MIL-101 (Cr) S-1 composite material;
Fig. 5 is the high rate performance figure of the embodiment of the invention one MIL-101 (Cr) S-1 composite material;
Fig. 6 is 0.1C (168 mA/g) the multiplying power cycle performance figure of the embodiment of the invention one MIL-101 (Cr) S-1 composite material;
Fig. 7 is 0.8C (1344 mA/g) the multiplying power cycle performance figure of the embodiment of the invention one MIL-101 (Cr) S-1 composite material.
Embodiment
Below, specify the present invention through exemplary embodiment.Should be appreciated that scope of the present invention should not be limited to the scope of embodiment.Any variation or change that does not depart from purport of the present invention can be understood by those skilled in the art.Protection scope of the present invention is confirmed by the scope of accompanying claims.
Cr (NO with 2.0 g
3)
39H
2The terephthalic acids H of O and 0.833 g
2BDC is dissolved in the 30 mL deionized waters, adds the HF of 0.26 mL again, fully after the dissolving solution is moved in the polytetrafluoroethylene retort of 50 mL capacity, again retort is placed stainless steel outer sleeve and sealing; Retort is put into the temperature programming stove carry out hydro-thermal reaction, heating schedule is: with 5.0 oC/min solution is heated to 210 oC from room temperature, and keeps 8 h, with the rate of temperature fall of 0.4 oC/min solution is reduced to room temperature more afterwards; After treating that solution is cooled to room temperature, with crystal wash successively, dimethyl formamide (DMF) is washed and to wash the back centrifugal for ethanol, filters, drying makes MIL-101 (Cr) metal-organic framework materials.With part by weight is sulphur and MIL-101 (Cr) ball mill mixing of 1.6 S/1.0 MIL-101 (Cr), and ball milling condition is: rotating speed is 250 commentaries on classics/min; The ball milling time is 6 hours.Then, the powder behind the ball milling is put into the temperature programming stove heat-treat, heat treated condition is: rise to 150 oC with the speed of 0.3 oC/min from room temperature and keep 1 h; Reduce to room temperature with the speed of 5 oC/min again.Finally obtain MIL-101 (Cr) S-1 composite material.
Embodiment 2
Cr (NO with 2.2 g
3)
39H
2The terephthalic acids H of O and 0.905 g
2BDC is dissolved in the 40 mL deionized waters, adds the HF of 0.28 mL again, fully after the dissolving solution is moved in the polytetrafluoroethylene retort of 100 mL capacity, again retort is placed stainless steel outer sleeve and sealing; Retort is put into the temperature programming stove carry out hydro-thermal reaction, heating schedule is: with 8.0 oC/min solution is heated to 215 oC from room temperature, and keeps 9 h, with the rate of temperature fall of 0.5 oC/min solution is reduced to room temperature more afterwards; After treating that solution is cooled to room temperature, with crystal wash successively, dimethyl formamide (DMF) is washed and to wash the back centrifugal for ethanol, filters, drying makes MIL-101 (Cr) metal-organic framework materials.With part by weight is sulphur and MIL-101 (Cr) ball mill mixing of 2.5 S/1.0 MIL-101 (Cr), and ball milling condition is: rotating speed is 350 commentaries on classics/min; The ball milling time is 4 hours.Then, the powder behind the ball milling is put into the temperature programming stove heat-treat, heat treated condition is: rise to 175 oC with the speed of 0.8 oC/min from room temperature and keep 1 h; Reduce to room temperature with the speed of 8 oC/min again.Finally obtain MIL-101 (Cr) S-2 composite material.
Embodiment 3
Cr (NO with 2.4 g
3)
39H
2The terephthalic acids H of O and 0.996 g
2BDC is dissolved in the 50 mL deionized waters, adds the HF of 0.30 mL again, fully after the dissolving solution is moved in the polytetrafluoroethylene retort of 100 mL capacity, again retort is placed stainless steel outer sleeve and sealing; Retort is put into the temperature programming stove carry out hydro-thermal reaction, heating schedule is: with 10.0 oC/min solution is heated to 220 oC from room temperature, and keeps 10 h, with the rate of temperature fall of 0.6 oC/min solution is reduced to room temperature more afterwards; After treating that solution is cooled to room temperature, with crystal wash successively, dimethyl formamide (DMF) is washed and to wash the back centrifugal for ethanol, filters, drying makes MIL-101 (Cr) metal-organic framework materials.With part by weight is sulphur and MIL-101 (Cr) ball mill mixing of 3.2 S/1.0 MIL-101 (Cr), and ball milling condition is: rotating speed is 400 commentaries on classics/min; The ball milling time is 2 hours.Then, the powder behind the ball milling is put into the temperature programming stove heat-treat, heat treated condition is: rise to 200 oC with the speed of 1.0 oC/min from room temperature and keep 1 h; Reduce to room temperature with the speed of 10 oC/min again.Finally obtain MIL-101 (Cr) S-3 composite material.
Instance analysis
The thermogravimetric curve and the surface topography of MIL-101 (Cr) S composite material
Adopt the comprehensive thermal analyzer of STA449C type that German NETZSCH company produces that MIL-101 (Cr) the S composite material of the present invention's preparation is carried out heat stability testing; In baking oven, carry out weightlessness analysis behind the dry 4h down before the testing of materials in 100 ℃; Test condition is: nitrogen protection; Heating rate is 10 ℃/min, and the intensification scope is 25 ~ 600 ℃, and the result is as shown in Figure 1.
As shown in Figure 1; The weightlessness of MIL-101 (Cr) S composite material under 280 ° of C of the present invention's preparation is about 60%; This part weight is sulphur components contents in MIL-101 (Cr) the S composite material (decomposition temperature of MIL-101 crystal begins to be 275-280 ° of C approximately), this shows that the sulfur content of MIL-101 (Cr) S composite material is about 60%.In addition; Compare with the weight-loss curve of bright sulfur; Sulphur component in MIL-101 (Cr) the S composite material more is prone to from MIL-101 (Cr) skeleton, deviate from, and this shows, the boiling point step-down of the sulphur component in MIL-101 (Cr) material; The granularity that sulfur granules is described diminishes, and the SEM photo result of this and MIL-101 (Cr) S composite material meets very much.By shown in Figure 2, particle surface is not seen tangible sulfur granules, and sulphur comparatively even at MIL-101 (Cr) material load is described, soaks within the duct.
Composite material pore structure property representation
The ASAP-2010 specific surface pore-size distribution appearance that adopts U.S. Micro company to produce characterizes MIL-101 (Cr) metal-organic framework materials of the present invention's preparation and the pore structure of MIL-101 (Cr) S composite material, and the result is shown in Fig. 3 and table 1.
The pore structure parameter of table 1 MIL-101 (Cr) and MIL-101 (Cr) S composite material
| Materials | S BET (m 2/g) | S Langmuir (m 2/g) | V Totle (cm 3/g) |
| MIL-101 | 3483.9 | 5071.1 | 1.86 |
| MIL-101S | 12.8 | 21.8 | 0.024 |
Can find out by Fig. 3 and table 1, after the present invention loads to MIL-101 (Cr) metal-organic framework materials through fusion-diffusion-absorption method with the sulphur component, make Langmuir specific area and the pore volume of MIL-101 (Cr) material from 5071.1 m
2/ g and 1.86 cm
3/ g drops to 21.8 m
2/ g and 0.024 cm
3/ g.This explanation, active component sulphur are fully filled and are got among MIL-101 (Cr) duct, thereby, cause sharply reducing of porous material MIL-101 (Cr) specific area and pore volume.
Chemical property as the positive electrode of lithium-sulfur cell
Fig. 4 shows anode MIL-101 (Cr) S composite material at multiplying power 0.1C, 0.2C, 0.5C and 0.8C (1C=1680mAhg
-1) under charging and discharging curve.Can find out from the rate charge-discharge curve of battery, along with the variation of multiplying power, the discharge platform of battery remain two (～2.3V with～2.1V), the Stability Analysis of Structures of MIL-101 (Cr) S composite material has been described, help keeping the high-energy-density of battery.
Fig. 5 shows the high rate performance figure of MIL-101 (Cr) S composite material under different discharge-rate 0.1C, 0.2C, 0.5C and 0.8C.By shown in Figure 5, the specific discharge capacity of battery under 0.1C, 0.2C, 0.5C and 1.0C is followed successively by 760,690,542 and 433 mAh/g; When discharge-rate when 1.0 are reduced to 0.1C, the specific discharge capacity of material increases to 716 mAh/g from 433 mAh/g.Simultaneously, along with the increase of discharge-rate, the enclosed pasture efficient of material has the trend of increase.This shows that material is at test multiplying power change procedure, the cyclic curve of material is steady, and discharge capacity is restorative good, has embodied the high specific discharge capacity and the excellent high rate performance of this material fully.
It is the cycle performance figure under 0.1C and the 0.8C at discharge-rate that Fig. 6 and Fig. 7 show MIL-101 (Cr) S composite material.As shown in the figure, material is behind 100 circles of circulation under the discharge-rate of 0.1C and 0.8C and 120 circles, and its specific discharge capacity remains on 692 and 386 mAh/g respectively, and its capability retention is respectively 91.1 and 85.7%.This explanation, the MIL-101 (Cr) in MIL-101 (Cr) the S composite material has played the effect of solid sulphur well, and material is repeatedly still keeping higher capacity after the circulation.
Claims (4)
1. adopt the fusion diffusion method to prepare the preparation method of metallic organic framework MIL-101 (Cr) the S composite material of high power capacity and excellent cycle performance; It is characterized in that: utilize with specific area, the hole of MIL-101 (Cr) superelevation warm regular in the three-dimensional framework structure of little diplopore; The sulphur component is adsorbed among the duct with the form of nano particle; Play solid sulphur and the double action of disperseing sulphur; With dissolving the caused battery capacity decay too fast problem of active component sulphur in the positive electrode that solves lithium-sulfur cell in electrolyte, comprise the steps:
(1) MIL-101 (Cr) metal-organic framework materials is synthetic:
Cr (NO with 2.0-2.4 g
3)
39H
2The terephthalic acids H of O and 0.833-0.996 g
2BDC is dissolved in the 30-50mL deionized water, adds the HF of 0.26-0.30 mL again, fully after the dissolving solution is moved in the polytetrafluoroethylene retort of 50-100 mL capacity, again retort is placed stainless steel outer sleeve and sealing; Retort is put into the temperature programming stove carry out hydro-thermal reaction, heating schedule is: with 5-10 oC/min solution is heated to 210-220 oC from room temperature, and keeps 8-10 h, with the rate of temperature fall of 0.4-0.6 oC/min solution is reduced to room temperature more afterwards; After treating that solution is cooled to room temperature, with crystal wash successively, dimethyl formamide (DMF) is washed and to wash the back centrifugal for ethanol, filters, drying makes MIL-101 (Cr) metal-organic framework materials
(2) preparation of metallic organic framework MIL-101 (Cr) S composite material:
With part by weight is sulphur and MIL-101 (Cr) ball mill mixing of (1.6-3.2) S/1.0MIL-101 (Cr), then the powder behind the ball milling is put into the temperature programming stove and heat-treats, and finally obtains MIL-101 (Cr) S composite material.
2. preparation method according to claim 1 is characterized in that: the weight ratio of said sulphur of step (2) and MIL-101 (Cr) is: 1.6-3.2/1.0.
3. preparation method according to claim 1 is characterized in that, in the step (2), said ball milling condition is: rotating speed is 250-400 commentaries on classics/min; The ball milling time is 2-6 hour.
4. according to the preparation method described in the claim 1, it is characterized in that in the step (2), the process of said temperature programming may further comprise the steps:
(1) temperature-rise period: rise to 150-200 oC from room temperature with the speed of the 0.3-1.0 oC/min powder after with ball milling;
(2) thermostatic process: the mixture of MIL-101 (Cr) and sulphur is kept 1-3 h at 150-200 oC;
(3) temperature-fall period: the speed with 5-10 oC/min is reduced to room temperature with precursor solution from 150-200 oC.
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102938475A (en) * | 2012-11-08 | 2013-02-20 | 中国科学院化学研究所 | Sodium-sulfur battery and manufacture method thereof |
| CN103151543A (en) * | 2013-03-04 | 2013-06-12 | 北京化工大学常州先进材料研究院 | Mn-M/MOFs catalyst for lithium-air battery and preparation method |
| CN103165912A (en) * | 2013-02-28 | 2013-06-19 | 北京化工大学常州先进材料研究院 | Catalytic agent for lithium-air battery cathode and preparation method |
| CN104332600A (en) * | 2014-10-24 | 2015-02-04 | 东莞市翔丰华电池材料有限公司 | Method for preparing graphene/sulfur/conductive polymer composite material used for lithium-sulfur battery positive electrode |
| KR20160021156A (en) * | 2016-01-25 | 2016-02-24 | 인하대학교 산학협력단 | Manufacturing method of chromium-based metal organic frameworks |
| CN106207135A (en) * | 2016-09-09 | 2016-12-07 | 广西大学 | A kind of Bombyx mori L. porous charcoal/MILs composite sulfur positive electrode and preparation method thereof |
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| CN110420661A (en) * | 2019-08-15 | 2019-11-08 | 山东大学 | In-situ preparation MIL-101 (Fe) composite catalyzing material and the preparation method and application thereof on a kind of 3D-rGO |
| CN111686694A (en) * | 2019-03-15 | 2020-09-22 | 中国石油化工股份有限公司 | Preparation method and application of MIL-101 material |
| CN111900456A (en) * | 2020-07-27 | 2020-11-06 | 珠海冠宇电池股份有限公司 | Composite positive pole piece, preparation method thereof and all-solid-state lithium ion battery |
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102268044A (en) * | 2011-06-02 | 2011-12-07 | 南京工业大学 | Method for synthesizing pure metal organic skeleton MIL-101 by one-step process |
-
2012
- 2012-07-08 CN CN2012102336249A patent/CN102751492A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102268044A (en) * | 2011-06-02 | 2011-12-07 | 南京工业大学 | Method for synthesizing pure metal organic skeleton MIL-101 by one-step process |
Non-Patent Citations (3)
| Title |
|---|
| G.FEREY,ET AL.: "A Chromium Terephthalate-Based Solid with Unusually Large Pore Volumes and Surface Area", 《SCIENCE》 * |
| JIAO SHI,ET AL.: "Adsorption and Diffusion of Ethyl Acetate on the Chromium-Based Metal-Organic Framework MIL-101", 《JOURNAL OF CHEMICAL & ENGINEERING DATA》 * |
| REZAN DEMIR-CAKAN,ET AL.: "Cathode Composites for Li-S Batteries via the Use of Oxygenated Porous Architectures", 《J. AM. CHEM. SOC.》 * |
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| CN103165912A (en) * | 2013-02-28 | 2013-06-19 | 北京化工大学常州先进材料研究院 | Catalytic agent for lithium-air battery cathode and preparation method |
| CN103151543A (en) * | 2013-03-04 | 2013-06-12 | 北京化工大学常州先进材料研究院 | Mn-M/MOFs catalyst for lithium-air battery and preparation method |
| CN104332600A (en) * | 2014-10-24 | 2015-02-04 | 东莞市翔丰华电池材料有限公司 | Method for preparing graphene/sulfur/conductive polymer composite material used for lithium-sulfur battery positive electrode |
| KR20160021156A (en) * | 2016-01-25 | 2016-02-24 | 인하대학교 산학협력단 | Manufacturing method of chromium-based metal organic frameworks |
| KR101616078B1 (en) | 2016-01-25 | 2016-04-29 | 인하대학교 산학협력단 | Manufacturing method of chromium-based metal organic frameworks |
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| CN106207135A (en) * | 2016-09-09 | 2016-12-07 | 广西大学 | A kind of Bombyx mori L. porous charcoal/MILs composite sulfur positive electrode and preparation method thereof |
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| CN108126755B (en) * | 2018-01-31 | 2020-09-15 | 中国民航大学 | Preparation method of fluorine/chlorine exchange catalyst based on modified MOF |
| CN111686694A (en) * | 2019-03-15 | 2020-09-22 | 中国石油化工股份有限公司 | Preparation method and application of MIL-101 material |
| CN110420661A (en) * | 2019-08-15 | 2019-11-08 | 山东大学 | In-situ preparation MIL-101 (Fe) composite catalyzing material and the preparation method and application thereof on a kind of 3D-rGO |
| CN113394368A (en) * | 2020-03-11 | 2021-09-14 | 宁德新能源科技有限公司 | Pole piece and electrochemical device |
| CN113394368B (en) * | 2020-03-11 | 2023-08-01 | 宁德新能源科技有限公司 | Pole piece and electrochemical device |
| CN111900456A (en) * | 2020-07-27 | 2020-11-06 | 珠海冠宇电池股份有限公司 | Composite positive pole piece, preparation method thereof and all-solid-state lithium ion battery |
| CN111900456B (en) * | 2020-07-27 | 2021-11-16 | 珠海冠宇电池股份有限公司 | Composite positive pole piece, preparation method thereof and all-solid-state lithium ion battery |
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