CN104129815A - Synthesis method and use of monodispersed KMn8O16 nanospheres - Google Patents

Synthesis method and use of monodispersed KMn8O16 nanospheres Download PDF

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CN104129815A
CN104129815A CN201410359884.XA CN201410359884A CN104129815A CN 104129815 A CN104129815 A CN 104129815A CN 201410359884 A CN201410359884 A CN 201410359884A CN 104129815 A CN104129815 A CN 104129815A
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kmn
disperses
nanometer ball
manganese oxygen
kmn8o16
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CN104129815B (en
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李昱
黄绍专
蔡祎
金俊
张倩
王洪恩
苏宝连
阳晓宇
陈丽华
邓兆
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Wuhan University of Technology WUT
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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 a synthesis method and a use of monodispersed KMn8O16 nanospheres. The synthesis method of the monodispersed KMn8O16 nanospheres comprises the following steps of dissolving potassium permanganate, polyvinylpyrrolidone and carbonate in deionized water, adding soluble organic alcohol into the solution, carrying out mixing to obtain a uniform mixture, putting the mixture into a thermostatic bath, carrying out a thermostatic reaction process at a temperature of 50-120 DEG C for 1-24h to obtain brownish black precipitates, drying the brownish black precipitates, and calcining the dried brownish black precipitates in an argon atmosphere at a temperature of 300-600 DEG C for 2-20h to obtain the monodispersed KMn8O16 nanospheres. The monodispersed KMn8O16 nanospheres have structured morphology and uniform size adjustable in a range of 80-200nm. The monodispersed KMn8O16 nanospheres are prepared by a constant-temperature liquid phase reaction. The synthesis method is easy and simple and has a large yield. A performance test shows that the monodispersed KMn8O16 nanospheres have a large application prospect in the lithium ion battery energy storage field.

Description

A kind of single potassium manganese oxygen KMn that disperses 8o 16the synthetic method of nanometer ball and application thereof
Technical field
The present invention relates to a kind of single potassium manganese oxygen KMn that disperses 8o 16the synthetic method of nanometer ball and application thereof, belong to inorganic material chemistry preparing technical field.
Background technology
Potassium manganese oxygen (KMn 8o 16) belong to tetragonal phase structure, be a kind of manganese oxide of potassium manganese ore type, this material has the manganese of mixing valence state, and has tunnel structure.In recent years, potassium manganese oxygen has been obtained widespread use at aspects such as catalysis, photochemical catalysis, gas sensing, drug release and energy storages, particularly aspect energy storage, has received increasing concern.Because potassium manganese oxygenate becomes easily, thermostability is high, and has tunnel effect, and the positive electrode material that someone has started it as lithium ion battery is tested, but not yet occurs the report using it as battery cathode.
At present, people improve its storage lithium performance by regulating and controlling surface properties, size and the pattern of potassium manganese oxygen.There is report or the patent of being correlated with in the structures such as the nano particle of potassium manganese oxygen, nano wire, nanometer rod, nano belt.The people such as Wang Shi's spring professor of Hubei University utilize hydrothermal method to synthesize potassium manganese oxygen nanometer rod, and be made into electrode test handling property (J.Nanosci.Nanotechnol.2013,13,2814-2818).Although there is in recent years the preparation of relevant potassium manganese oxygen and be applied to the report that lithium ion battery electrode material is studied, but above-mentioned report adopts hydrothermal method mostly, and in reaction process, adopt potassium permanganate as oxygenant, bivalent manganese as reductive agent, react that temperature required height, time are long, output is very low, be unfavorable for the large-scale application in actual production.
Summary of the invention
Technical problem to be solved by this invention is the deficiency existing for above-mentioned prior art, and a kind of single potassium manganese oxygen KMn that disperses is provided 8o 16the synthetic method of nanometer ball and application thereof, the raw material in the more existing report of raw material that the method relates to is more common, and preparation method is simple, repeatability is high, and output is large, by the single potassium manganese oxygen KMn that disperses making 8o 16nanometer ball is applied to lithium ion cell electrode, shows good chemical property.
For achieving the above object, the technical solution used in the present invention is:
A kind of single potassium manganese oxygen KMn that disperses 8o 16the synthetic method of nanometer ball, comprises following steps successively:
(1) in deionized water, add potassium permanganate, soluble carbonate salt and polyvinylpyrrolidone PVP, preparation potassium permanganate concentration is 0.01～0.5mol/L, and carbonate concentration is 0.02～1mol/L, the homogeneous aqueous solution that PVP concentration is 0.2～5g/L;
(2) in the aqueous solution of step (1) preparation, add solubility Organic Alcohol, form uniform mixing solutions, the volume ratio of Organic Alcohol and the aqueous solution is (0.5～4): 1;
(3) mixing solutions step (2) being obtained is placed in the system of opening wide, and at 50～120 ℃ of isothermal reaction 1～24h, obtains brownish black precipitation;
(4) the brownish black precipitation obtaining is carried out, after eccentric cleaning, drying to obtain brown-black powder;
(5) brown-black powder obtaining is placed in to tube furnace, in argon gas atmosphere, is warming up to 300～600 ℃ of calcining 2～20h, obtain described single KMn of dispersion 8o 16nanometer ball.
According to such scheme, described carbonate is that one or more of bicarbonate of ammonia, volatile salt and salt of wormwood are mixed in any proportion.
According to such scheme, the molecular weight of described polyvinylpyrrolidone is K28～K32.
According to such scheme, one or more that described solubility Organic Alcohol is anhydrous methanol, dehydrated alcohol and Virahol are mixed in any proportion.
According to such scheme, described unlimited system is to cover reaction vessel bottleneck with preservative film, and preservative film and bottleneck leave gap, makes reaction system keep communicating with atmosphere, prevents the too fast evaporation of Organic Alcohol.
According to such scheme, the preferred temperature of described isothermal reaction is 70～90 ℃; Preferably constant temperature time is 3～8h; The preferred heat-up rate of described calcination process is 2 ℃/min, and preferred calcination temperature is 350～550 ℃, and preferably calcination time is 2～8h.
According to such scheme, the single potassium manganese oxygen KMn that disperses making 8o 16nanometer ball pattern is regular, size homogeneous, and size is adjustable within the scope of 80～200nm.
Single potassium manganese oxygen KMn that disperses that above-mentioned preparation method makes 8o 16nanometer ball is applied to prepare the negative pole of lithium ion battery, shows good chemical property.
Compared with prior art, the invention has the beneficial effects as follows:
(1) the present invention uses potassium permanganate, carbonate and solubility Organic Alcohol are conventional chemical reagent, do not use other poisonous and hazardous organic surface active agent and additives.
(2) the present invention adopts Organic Alcohol as reductive agent, utilizes the synthetic potassium manganese oxygen nanometer ball of low temperature liquid phase reaction, and the reaction conditions relating to is simple, repeatability is high.
(3) reaction the present invention relates to low temperature on thermostatic bath carries out, less energy consumption, and to reaction vessel, there is no particular limitation, reaction safety and stability, output is very large, meets the requirement of production application.
(4) single potassium manganese oxygen KMn that disperses that prepared by the present invention 8o 16nanometer ball pattern is regular, and size homogeneous is adjustable, has good monodispersity, shows outstanding thermostability in rare gas element and air.
(5) the single potassium manganese oxygen KMn that disperses being prepared by the present invention 8o 16nanometer ball is applied to prepare lithium ion cell electrode, shows outstanding lithium ion battery negative material performance.
Accompanying drawing explanation
Below in conjunction with accompanying drawing, the invention will be further described, in accompanying drawing:
Fig. 1 is the single potassium manganese oxygen KMn that disperses making in the embodiment of the present invention 1 8o 16the XRD figure of nanometer ball.
Fig. 2 is the single potassium manganese oxygen KMn that disperses making in the embodiment of the present invention 1 8o 16the SEM figure of nanometer ball.
Fig. 3 is the single potassium manganese oxygen KMn that disperses making in the embodiment of the present invention 2 8o 16the XRD figure of nanometer ball.
Fig. 4 is the single potassium manganese oxygen KMn that disperses making in the embodiment of the present invention 2 8o 16the SEM figure of nanometer ball.
Fig. 5 is the single potassium manganese oxygen KMn that disperses making in the embodiment of the present invention 3 8o 16the SEM figure of nanometer ball.
Fig. 6 is the single potassium manganese oxygen KMn that disperses making in the embodiment of the present invention 4 8o 16the XRD figure of nanometer ball.
Fig. 7 is the single potassium manganese oxygen KMn that disperses making in the embodiment of the present invention 4 8o 16the SEM figure of nanometer ball.
Fig. 8 is the single potassium manganese oxygen KMn that disperses making in the embodiment of the present invention 5 8o 16the SEM figure of nanometer ball.
Embodiment
For making object of the present invention, technical scheme and advantage clearer, below in conjunction with drawings and Examples, the present invention is further elaborated.Should be appreciated that specific embodiment described herein, only in order to explain the present invention, is not intended to limit the present invention.
In following examples, the carbonate of use is bicarbonate of ammonia, but other carbonate all can be realized the present invention as volatile salt, salt of wormwood, also can select the mixture of above-mentioned several carbonate; The weight molecule amount of the polyvinylpyrrolidone using other polyvinylpyrrolidone between K28～K32 all can be realized the present invention, also can select the mixture of above-mentioned several molecular weight polyethylene pyrrolidone; The solubility organic solvent using is Virahol, and other organic solvents all can be realized the present invention as dehydrated alcohol and anhydrous methanol, also can select the mixture of above-mentioned several organic solvents.
Embodiment 1
A kind of single potassium manganese oxygen KMn that disperses 8o 16the synthetic method of nanometer ball, comprises the following steps:
(1) take 0.003mol (0.474g) potassium permanganate, 0.015mol (1.185g) bicarbonate of ammonia and 0.1g polyvinylpyrrolidone (K29) and add in 35mL deionized water, stir 30min, obtain uniform purple clear solution;
(2) in the purple clear solution of step (1) preparation, add 70ml Virahol, stir 15min, form homogeneous mixture solotion;
(3) homogeneous mixture solotion step (2) being obtained is transferred in the beaker of 500mL, with preservative film, cover beaker (preservative film and beaker mouth leave gap), be placed in stirring (rotating speed is 1200r/min) on oil bath pan, from room temperature, begin to warm to 80 ℃, then at 80 ℃ of isothermal reaction 5h, then naturally cooling, obtains brownish black precipitation;
(4) the brownish black precipitation obtaining is placed in to water and ethanol on whizzer and alternately respectively cleans four times, centrifugal rotational speed is 6000r/min, then by the centrifugal product obtaining 60 ℃ of oven for drying, obtain brown-black powder;
(5) brown-black powder oven dry being obtained is placed in tube furnace, under argon gas atmosphere, calcines.Calcination process is: from room temperature, with the speed of 2 ℃/min, be warmed up to 400 ℃, and at 400 ℃ of insulation 4h, obtain described single potassium manganese oxygen KMn that disperses 8o 16nanometer ball.
The product that the present embodiment makes is defined as Tetragonal potassium manganese oxygen crystal (KMn through X-ray diffraction analysis 8o 16), its X-ray diffractogram is shown in Fig. 1; Scanning electronic microscope (SEM) analytical results shows, it is regular spherical that the pattern of products therefrom is, and has good monodispersity, and particle size is about 150nm, and its SEM figure is shown in Fig. 2.
Single potassium manganese oxygen KMn that disperses that the present embodiment is made 8o 16nanometer ball is applied to prepare the negative pole of lithium ion battery, show good chemical property: the result demonstration of button half-cell test, under the current density of 100mA/g, the first circle specific discharge capacity of battery is up to 1768mAh/g, after discharging and recharging 50 circles, reversible specific capacity still has 891mAh/g.
Embodiment 2:
A kind of single potassium manganese oxygen KMn that disperses 8o 16the synthetic method of nanometer ball, comprises the following steps:
(1) take 0.003mol (0.474g) potassium permanganate, 0.015mol (1.185g) bicarbonate of ammonia and 0.1g polyvinylpyrrolidone (K29) and join in 50mL deionized water, stir 30min, obtain uniform purple clear solution;
(2) in the purple clear solution of step (1) preparation, add 70ml Virahol, stir 15min, form homogeneous mixture solotion.
(3) homogeneous mixture solotion step (2) being obtained is transferred in the beaker of 500mL, with preservative film, cover beaker (preservative film and beaker mouth leave gap), be placed in stirring (rotating speed is 1200r/min) on oil bath pan, from room temperature, begin to warm to 80 ℃, then at 80 ℃ of isothermal reaction 5h, then naturally cooling, obtains brownish black precipitation;
(4) the brownish black precipitation obtaining is placed in to water and ethanol on whizzer and alternately respectively cleans four times, centrifugal rotational speed is 6000r/min, then by the centrifugal product obtaining 60 ℃ of oven for drying, obtain brown-black powder;
(5) brown-black powder oven dry being obtained is placed in tube furnace, under argon gas atmosphere, calcines.Calcination process is, from room temperature, is warmed up to 350 ℃, and at 350 ℃ of insulation 6h, obtains described single potassium manganese oxygen KMn that disperses with the speed of 2 ℃/min 8o 16nanometer ball.
The product that the present embodiment makes is defined as Tetragonal potassium manganese oxygen crystal (KMn through X-ray diffraction analysis 8o 16), its X-ray diffractogram is shown in Fig. 3; Scanning electronic microscope (SEM) analytical results shows, it is regular spherical that the pattern of products therefrom is, and has good monodispersity, and particle size is about 150nm, and its SEM figure is shown in Fig. 4.
Single potassium manganese oxygen KMn that disperses that the present embodiment is made 8o 16nanometer ball is applied to prepare the negative pole of lithium ion battery, show good chemical property: the result demonstration of button half-cell test, under the current density of 100mA/g, the first circle specific discharge capacity of battery is up to 1680mAh/g, after discharging and recharging 50 circles, reversible specific capacity still has 450mAh/g.
Embodiment 3:
A kind of single potassium manganese oxygen KMn that disperses 8o 16the synthetic method of nanometer ball, comprises the following steps:
(1) take 0.003mol (0.474g) potassium permanganate, 0.015mol (1.185g) bicarbonate of ammonia and 0.1g polyvinylpyrrolidone (K32) and join in 35mL deionized water, stir 30min, obtain uniform purple clear solution;
(2) in the purple clear solution of step (1) preparation, add 70ml Virahol, stir 15min, form homogeneous mixture solotion.
(3) homogeneous mixture solotion step (2) being obtained is transferred in the beaker of 500mL, with preservative film, cover beaker (preservative film and beaker mouth leave gap), be placed in stirring (rotating speed is 1200r/min) on oil bath pan, from room temperature, begin to warm to 60 ℃, then at 60 ℃ of isothermal reaction 5h, then naturally cooling, obtains brownish black precipitation;
(4) the brownish black precipitation obtaining is placed in to water and ethanol on whizzer and alternately respectively cleans four times, centrifugal rotational speed is 6000r/min, then by the centrifugal product obtaining 60 ℃ of oven for drying, obtain brown-black powder;
(5) brown-black powder oven dry being obtained is placed in tube furnace, under argon gas atmosphere, calcines.Calcination process is, from room temperature, is warmed up to 450 ℃, and at 450 ℃ of insulation 6h, obtains described single potassium manganese oxygen KMn that disperses with the speed of 2 ℃/min 8o 16nanometer ball.
The product that the present embodiment makes is defined as Tetragonal potassium manganese oxygen crystal (KMn through X-ray diffraction 8o 16); Scanning electronic microscope (SEM) analytical results shows, it is regular spherical that the pattern of products therefrom is, and has good monodispersity, and particle size is about 130nm, and its SEM figure is shown in Fig. 5.
Single potassium manganese oxygen KMn that disperses that the present embodiment is made 8o 16nanometer ball is applied to prepare the negative pole of lithium ion battery, show good chemical property: the result demonstration of button half-cell test, under the current density of 100mA/g, the first circle specific discharge capacity of battery is up to 2150mAh/g, after discharging and recharging 50 circles, reversible specific capacity still has 650mAh/g.
Embodiment 4
A kind of single potassium manganese oxygen KMn that disperses 8o 16the synthetic method of nanometer ball, comprises the following steps:
(1) take 0.003mol (0.474g) potassium permanganate, 0.015mol (1.185g) bicarbonate of ammonia and 0.05g polyvinylpyrrolidone (K32) and join in 35mL deionized water, stir 30min, obtain uniform purple clear solution;
(2) in the purple clear solution of step (1) preparation, add 70ml ethanol, stir 15min, form homogeneous mixture solotion.
(3) homogeneous mixture solotion step (2) being obtained is transferred in the beaker of 500mL, with preservative film, cover beaker (preservative film and beaker mouth leave gap), be placed in stirring (rotating speed is 1200r/min) on oil bath pan, from room temperature, begin to warm to 80 ℃, then at 80 ℃ of isothermal reaction 5h, then naturally cooling, obtains brownish black precipitation;
(4) the brownish black precipitation obtaining is placed in to water and ethanol on whizzer and alternately respectively cleans four times, centrifugal rotational speed is 6000r/min, then by the centrifugal product obtaining 60 ℃ of oven for drying, obtain brown-black powder;
(5) brown-black powder oven dry being obtained is placed in tube furnace, under argon gas atmosphere, calcines.Calcination process is, from room temperature, is warmed up to 400 ℃, and at 400 ℃ of insulation 4h, obtains described single potassium manganese oxygen KMn that disperses with the speed of 2 ℃/min 8o 16nanometer ball.
The product that the present embodiment makes is defined as Tetragonal potassium manganese oxygen crystal (KMn through X-ray diffraction analysis 8o 16), its X-ray diffractogram is shown in Fig. 6; Scanning electronic microscope (SEM) analytical results shows, it is regular spherical that the pattern of products therefrom is, and has good monodispersity, and particle size is about 80nm, and its SEM figure is shown in Fig. 7.
Embodiment 5
A kind of single potassium manganese oxygen KMn that disperses 8o 16the synthetic method of nanometer ball, comprises the following steps:
(1) take 0.002mol (0.316g) potassium permanganate, 0.015mol (1.185g) sodium bicarbonate and 0.1g polyvinylpyrrolidone (K32) and join in 35mL deionized water, stir 30min, obtain uniform purple clear solution;
(2) in the purple clear solution of step (1) preparation, add 80ml anhydrous methanol, stir 15min, form homogeneous mixture solotion;
(3) homogeneous mixture solotion step (2) being obtained is transferred in the beaker of 500mL, with preservative film, cover beaker (preservative film and beaker mouth leave gap), be placed in stirring (rotating speed is 1200r/min) on oil bath pan, from room temperature, begin to warm to 50 ℃, then at 50 ℃ of isothermal reaction 3h, then naturally cooling, obtains brownish black precipitation;
(4) the brownish black precipitation obtaining is placed in to water and ethanol on whizzer and alternately respectively cleans four times, centrifugal rotational speed is 6000r/min, then by the centrifugal product obtaining 60 ℃ of oven for drying, obtain brown-black powder;
(5) brown-black powder oven dry being obtained is placed in tube furnace, under argon gas atmosphere, calcines.Calcination process is, from room temperature, is warmed up to 400 ℃, and at 400 ℃ of insulation 4h, obtains described single potassium manganese oxygen KMn that disperses with the speed of 2 ℃/min 8o 16nanometer ball.
The product that the present embodiment makes is defined as Tetragonal potassium manganese oxygen crystal (KMn through X-ray diffraction 8o 16); Scanning electronic microscope (SEM) analytical results shows, it is regular spherical that the pattern of products therefrom is, and has good monodispersity, and particle size is about 200nm, and its SEM figure is shown in Fig. 8.
Bound value, the interval value of each raw material that invention relates to can be realized the present invention, and lower limit value and the interval value of processing parameter of the present invention (as temperature, time etc.) can be realized the present invention, at this, do not enumerate embodiment.

Claims (7)

1. a list disperses potassium manganese oxygen KMn 8o 16the synthetic method of nanometer ball, is characterized in that, comprises successively following steps:
(1) in deionized water, add potassium permanganate, soluble carbonate salt and polyvinylpyrrolidone PVP, preparation potassium permanganate concentration is that 0.01～0.5mol/L, carbonate concentration are the homogeneous aqueous solution that 0.02～1mol/L, PVP concentration are 0.2～5g/L;
(2) in the aqueous solution of step (1) preparation, add solubility Organic Alcohol, form uniform mixing solutions, the volume ratio of Organic Alcohol and the aqueous solution is (0.5～4): 1;
(3) mixing solutions step (2) being obtained is placed in the system of opening wide, and at 50～120 ℃ of isothermal reaction 1～24h, obtains brownish black precipitation;
(4) the brownish black precipitation obtaining is carried out, after eccentric cleaning, drying to obtain brown-black powder;
(5) brown-black powder obtaining is placed in to tube furnace, in argon gas atmosphere, is warming up to 300～600 ℃ of calcining 2～20h, obtain described single KMn of dispersion 8o 16nanometer ball.
2. a kind of list according to claim 1 disperses potassium manganese oxygen KMn 8o 16the synthetic method of nanometer ball, is characterized in that, described carbonate is that one or more of bicarbonate of ammonia, volatile salt and salt of wormwood are mixed in any proportion.
3. a kind of list according to claim 1 disperses potassium manganese oxygen KMn 8o 16the synthetic method of nanometer ball, is characterized in that, the molecular weight of described polyvinylpyrrolidone is K28～K32.
4. a kind of list according to claim 1 disperses potassium manganese oxygen KMn 8o 16the synthetic method of nanometer ball, is characterized in that, one or more that described solubility Organic Alcohol is anhydrous methanol, dehydrated alcohol and Virahol are mixed in any proportion.
5. a kind of list according to claim 1 disperses potassium manganese oxygen KMn 8o 16the synthetic method of nanometer ball, is characterized in that, the temperature of described isothermal reaction is 70～90 ℃; Constant temperature time is 3～8h; The heat-up rate of described calcination process is 2 ℃/min, and calcining temperature is 350～550 ℃, and calcination time is 2～8h.
6. a kind of list according to claim 1 disperses potassium manganese oxygen KMn 8o 16the synthetic method of nanometer ball, is characterized in that, single potassium manganese oxygen KMn that disperses that described method makes 8o 16nanometer ball pattern is regular, size homogeneous, and size is adjustable at 80～200nm.
7. single potassium manganese oxygen KMn that disperses that a kind of synthetic method according to claim 1 makes 8o 16the application of nanometer ball in lithium ion battery negative.
CN201410359884.XA 2014-07-25 2014-07-25 A kind of single dispersing potassium manganese oxygen KMn 8o 16the synthetic method of nanometer ball and application thereof Expired - Fee Related CN104129815B (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108002444A (en) * 2017-11-30 2018-05-08 湘潭大学 A kind of KMn8O16The preparation method of positive electrode
CN114425363A (en) * 2020-10-14 2022-05-03 中国石油化工股份有限公司 Catalyst for producing low-carbon olefin by one-step method and preparation method and application thereof

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Publication number Priority date Publication date Assignee Title
US4433035A (en) * 1981-10-26 1984-02-21 Duracell Inc. Catalytic cathode composition for air-depolarized cell and method of preparation
CN101927179A (en) * 2010-07-09 2010-12-29 北京工业大学 OMS-2 catalyst used in elimination of benzene series at low temperature and preparation and application

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4433035A (en) * 1981-10-26 1984-02-21 Duracell Inc. Catalytic cathode composition for air-depolarized cell and method of preparation
CN101927179A (en) * 2010-07-09 2010-12-29 北京工业大学 OMS-2 catalyst used in elimination of benzene series at low temperature and preparation and application

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108002444A (en) * 2017-11-30 2018-05-08 湘潭大学 A kind of KMn8O16The preparation method of positive electrode
CN114425363A (en) * 2020-10-14 2022-05-03 中国石油化工股份有限公司 Catalyst for producing low-carbon olefin by one-step method and preparation method and application thereof
CN114425363B (en) * 2020-10-14 2023-08-29 中国石油化工股份有限公司 Catalyst for producing low-carbon olefin by one-step method, and preparation method and application thereof

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