CN115000363A - Organic matter/manganese-based oxide composite material and preparation method and application thereof - Google Patents
Organic matter/manganese-based oxide composite material and preparation method and application thereof Download PDFInfo
- Publication number
- CN115000363A CN115000363A CN202210522048.3A CN202210522048A CN115000363A CN 115000363 A CN115000363 A CN 115000363A CN 202210522048 A CN202210522048 A CN 202210522048A CN 115000363 A CN115000363 A CN 115000363A
- Authority
- CN
- China
- Prior art keywords
- manganese
- based oxide
- composite material
- organic
- oxide composite
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000011572 manganese Substances 0.000 title claims abstract description 139
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims abstract description 138
- 229910052748 manganese Inorganic materials 0.000 title claims abstract description 138
- 239000002131 composite material Substances 0.000 title claims abstract description 110
- 239000005416 organic matter Substances 0.000 title claims abstract description 58
- 238000002360 preparation method Methods 0.000 title abstract description 14
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 claims abstract description 38
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims abstract description 35
- VTWDKFNVVLAELH-UHFFFAOYSA-N 2-methylcyclohexa-2,5-diene-1,4-dione Chemical compound CC1=CC(=O)C=CC1=O VTWDKFNVVLAELH-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000012286 potassium permanganate Substances 0.000 claims abstract description 28
- 239000000178 monomer Substances 0.000 claims abstract description 22
- 229940071125 manganese acetate Drugs 0.000 claims abstract description 20
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical group [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims abstract description 20
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 14
- 150000002696 manganese Chemical class 0.000 claims abstract description 13
- 239000010405 anode material Substances 0.000 claims abstract description 7
- KXDAEFPNCMNJSK-UHFFFAOYSA-N Benzamide Chemical compound NC(=O)C1=CC=CC=C1 KXDAEFPNCMNJSK-UHFFFAOYSA-N 0.000 claims abstract description 6
- 230000035484 reaction time Effects 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims abstract description 4
- 229940099596 manganese sulfate Drugs 0.000 claims abstract description 4
- 235000007079 manganese sulphate Nutrition 0.000 claims abstract description 4
- 239000011702 manganese sulphate Substances 0.000 claims abstract description 4
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims abstract description 4
- 230000009471 action Effects 0.000 claims abstract description 3
- 238000013329 compounding Methods 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 39
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 28
- 239000007864 aqueous solution Substances 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 14
- 239000000843 powder Substances 0.000 claims description 14
- 239000008367 deionised water Substances 0.000 claims description 13
- 229910021641 deionized water Inorganic materials 0.000 claims description 13
- 239000011259 mixed solution Substances 0.000 claims description 13
- 239000007787 solid Substances 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 9
- 239000002033 PVDF binder Substances 0.000 claims description 6
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 6
- 239000002002 slurry Substances 0.000 claims description 6
- 238000004140 cleaning Methods 0.000 claims description 5
- 238000000576 coating method Methods 0.000 claims description 5
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical group CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 4
- 239000011230 binding agent Substances 0.000 claims description 4
- 239000011248 coating agent Substances 0.000 claims description 4
- 239000006258 conductive agent Substances 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- 239000006230 acetylene black Substances 0.000 claims description 3
- -1 polytetrafluoroethylene Polymers 0.000 claims description 3
- 239000006229 carbon black Substances 0.000 claims description 2
- 239000002041 carbon nanotube Substances 0.000 claims description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 2
- 229910001220 stainless steel Inorganic materials 0.000 claims description 2
- 239000010935 stainless steel Substances 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 238000009830 intercalation Methods 0.000 abstract description 8
- 230000002687 intercalation Effects 0.000 abstract description 8
- 239000002904 solvent Substances 0.000 abstract description 4
- 238000003837 high-temperature calcination Methods 0.000 abstract description 3
- 230000001276 controlling effect Effects 0.000 abstract description 2
- 230000003993 interaction Effects 0.000 abstract description 2
- 230000001105 regulatory effect Effects 0.000 abstract description 2
- 230000001939 inductive effect Effects 0.000 abstract 1
- 239000000463 material Substances 0.000 description 36
- 230000000052 comparative effect Effects 0.000 description 24
- 238000012360 testing method Methods 0.000 description 10
- 230000008569 process Effects 0.000 description 8
- 238000013112 stability test Methods 0.000 description 8
- 239000003792 electrolyte Substances 0.000 description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 5
- 238000001994 activation Methods 0.000 description 5
- 238000007599 discharging Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 102000004310 Ion Channels Human genes 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- 230000004913 activation Effects 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 229910001416 lithium ion Inorganic materials 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- 239000011247 coating layer Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 230000005012 migration Effects 0.000 description 3
- 238000013508 migration Methods 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 230000002572 peristaltic effect Effects 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- 239000013543 active substance Substances 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000009831 deintercalation Methods 0.000 description 2
- 238000000840 electrochemical analysis Methods 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 238000004880 explosion Methods 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000011368 organic material Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000002093 peripheral effect Effects 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- 239000002152 aqueous-organic solution Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- DCYOBGZUOMKFPA-UHFFFAOYSA-N iron(2+);iron(3+);octadecacyanide Chemical class [Fe+2].[Fe+2].[Fe+2].[Fe+3].[Fe+3].[Fe+3].[Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] DCYOBGZUOMKFPA-UHFFFAOYSA-N 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
-
- 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 relates to an organic matter/manganese-based oxide composite material and a preparation method and application thereof, belonging to the technical field of preparation of anode materials of water-system rechargeable zinc ion batteries. The composite material is prepared by compounding divalent manganese salt and an organic monomer by a hydrothermal method under the action of potassium permanganate, wherein the divalent manganese salt is manganese acetate or manganese sulfate, and the organic monomer is at least one of p-phenylenediamine, p-benzoquinone, methyl-p-benzoquinone and benzamide; introducing organic matter monomers in a hydrothermal kettle at high temperature and high pressure, and inducing intercalation of the organic matter in the manganese-based oxide through interaction between solvents; the organic matter/manganese-based oxide composite material with stable structure is obtained by regulating and controlling the temperature and time of the hydrothermal reaction and the concentration of the organic matter monomer; the preparation method can be completed only by one step of hydrothermal reaction, has low reaction temperature, short reaction time, simplicity and easy operation, and does not need high-temperature calcination; the composite material has excellent cycle stability and rate capability, and can be used as a zinc ion battery anode material.
Description
Technical Field
The invention relates to an organic matter/manganese-based oxide composite material and a preparation method and application thereof, belonging to the technical field of preparation of anode materials of water system rechargeable zinc ion batteries.
Background
Energy storage devices which are commercialized at present are applied in different scenes due to differences of use conditions, price, portability and the like. The sodium ion battery is mainly used for large-scale energy storage due to low manufacturing cost. The lithium ion battery has the advantages of long cycle life, high specific energy, no memory effect and the like, and is widely applied to electronic equipment and vehicles such as computers, mobile phones, electric automobiles and the like which are common in life. However, the electrolyte of the lithium ion battery is a non-aqueous organic solution, and when the battery is short-circuited, the lithium ion battery is very easy to cause fire and explosion. Moreover, metal materials such as lithium, cobalt and the like used by the lithium ion battery are expensive, and a waterless environment is required in the production process, so that the battery cost is further increased. Therefore, it is important to develop a novel secondary battery which is inexpensive and contains no or only a small amount of combustible materials.
The zinc ion battery has the following characteristics: the zinc metal has rich content, low price and environmental protection, and has the condition of large-scale development and application; the zinc ion battery has the characteristic of high power density, and can be suitable for application in special scenes; zn has low oxidation-reduction potential (-0.76V vs. NHE); the metal zinc has good compatibility with water, can use aqueous electrolyte, has no explosion risk, reduces the production environment requirement during assembly and reduces the cost; the theoretical specific capacity of zinc is up to 819mAh g -1 . In the water-based zinc ion battery, the positive electrode material mainly adopts manganese-based oxide, vanadium-based oxide, prussian blue analogue, organic matter and the like. The manganese-based oxides are of a wide variety, including alpha-MnO 2 、β-MnO 2 、γ-MnO 2 、Mn 3 O 4 And the like. The crystal structure of the manganese-based oxide is mostly layered or tunnel-shaped, and the structure is easy to collapse due to the embedding and the separation of zinc ions in the charge and discharge process of the battery; the needle-shaped structure of the manganese-based oxide is easy to agglomerate, an ion channel is blocked, the performance is poor under the condition of high current density, multiple times of charging and discharging activation are needed to reach a capacity peak value, the consumed time is long, the material has unsatisfactory cycle stability, the service life of the battery is short, and the application of the manganese-based oxide in a water system zinc ion battery is severely limited.
At present, the structural stability of the manganese-based oxide is improved by a method of coating a carbon layer on the surface of the manganese-based oxide, and the manganese-based oxide can be isolated from electrolyte by the coating layer outside the manganese-based oxide, so that the dissolution and structural change of manganese are limited. However, the method has the following disadvantages:
(1) the carbon coating layer can not store Zn in the charging and discharging process 2+ The composite material finally obtained has the mass ratio of about 20 percent, so that the material cannot provide capacity, and the capacity of the material is low; (2) along with the increase of the charging and discharging times of the battery, the coating layer of the coated composite material can be dissolved and fall off, so that the performance of the material is reduced; (3) the carbon coating process needs high-temperature calcination, and has high energy consumption, much time consumption and complex operation.
Disclosure of Invention
In order to overcome the defects in the prior art, one of the purposes of the invention is to provide an organic matter/manganese-based oxide composite material, wherein the composite material reduces the mass ratio of inactive substances and improves the mass ratio of active substances, so that the specific capacity of the composite material is improved.
The second purpose of the invention is to provide a preparation method of the organic matter/manganese-based oxide composite material.
The invention also aims to provide application of the organic matter/manganese-based oxide composite material.
In order to achieve the purpose of the invention, the following technical scheme is provided.
An organic matter/manganese-based oxide composite material is prepared by compounding divalent manganese salt and an organic matter monomer by a hydrothermal method under the action of potassium permanganate; based on the total mass of the organic matter/manganese-based oxide composite material as 100%, the mass fraction of the organic matter monomer is 1% -10%, and the mass fraction of the manganese-based oxide is 90% -99%;
the divalent manganese salt is manganese acetate or manganese sulfate;
the organic monomer is at least one of p-phenylenediamine, p-benzoquinone, methyl-p-benzoquinone and benzamide.
Preferably, the organic matter/manganese-based oxide is of a rod-shaped structure, and the length of the rod-shaped structure is 0.2-0.5 mu m;
preferably, the mass fraction of the organic monomer is 2-4% and the mass fraction of the manganese-based oxide is 96-98% based on 100% of the total mass of the organic/manganese-based oxide composite material.
The invention relates to a preparation method of an organic matter/manganese-based oxide composite material, which comprises the following steps:
(1) sequentially adding a sulfuric acid solution and organic matter monomer powder into a divalent manganese salt aqueous solution, and stirring until a uniform and clear solution A is obtained; the influence of the added sulfuric acid solution and the organic monomer powder on the volume of the manganese dioxide aqueous solution is ignored;
in the divalent manganese salt aqueous solution, the concentration of divalent manganese salt is 80-110 mmol/L;
in the solution A, the concentration of sulfuric acid is 66-73 mmol/L;
in the solution A, the concentration of organic monomer powder is 7.2-14.5 mmol/L;
(2) dropwise adding a potassium permanganate aqueous solution with the concentration of 63.2-96.6 mmol/L into the solution A obtained in the step (1) at the speed of 1-2 mL/min under the stirring condition of the speed of 300-600 r/min to obtain a mixed solution B;
the volume ratio of the solution A obtained in the step (1) to the potassium permanganate aqueous solution is 1: 0.53 to 0.67;
preferably, after the dropwise addition of the potassium permanganate solution is finished, the mixed solution B is continuously stirred at the speed of 300-600 r/min for 30-60 min;
(3) transferring the mixed solution B obtained in the step (2) to a hydrothermal kettle, wherein the reaction temperature is 110-130 ℃, and the reaction time is 12-18 h; obtaining a solid-liquid mixture, and separating, washing and drying the obtained solid to obtain the organic matter/manganese-based oxide composite material;
preferably, the solid obtained in the solid-liquid mixture is centrifugally washed and dried by deionized water.
The invention relates to an application of an organic matter/manganese-based oxide composite material, which is a zinc ion battery anode material.
The specific application method is as follows:
the organic matter/manganese-based oxide composite material, the conductive agent and the binder are mixed according to the mass ratio of (6.5-7): (2-3): (0.5-1) mixing and grinding, adding an organic solvent to form slurry, then coating the slurry on a current collector, and drying in an oven at the temperature of 60-80 ℃ to obtain the battery anode;
the conductive agent is acetylene black, carbon black, super P or carbon nano tube;
the binder is polyvinylidene fluoride or polytetrafluoroethylene;
the organic solvent is N-methyl pyrrolidone;
the current collector is a titanium foil or a stainless steel net.
Advantageous effects
(1) The invention provides an organic matter/manganese-based oxide composite material, wherein an organic matter monomer in the composite material is embedded into a crystal lattice of a manganese-based oxide in situ by a hydrothermal method, the organic matter and the manganese-based oxide are in a homogeneous phase, and the organic matter and the manganese-based oxide are not dissolved or dropped in the charge-discharge process of a zinc ion battery; the mass fraction of the organic monomer serving as the inactive substance in the composite material is 1-10%, compared with the mass fraction of the inactive substance in the carbon-coated composite material which is about 20%, the composite material remarkably reduces the mass fraction of the inactive substance and improves the mass fraction of the active substance, thereby overcoming the defect of low specific capacity of the material, and the initial specific capacity of the organic/manganese-based oxide composite material under 0.5 ℃ reaches 130 mAh.g -1 Above, the specific capacity can be kept at 195 mAh.g after activation -1 The above circulation is not less than 50 circles.
(2) The invention provides an organic matter/manganese-based oxide composite material, which is in a rod-shaped structure, has the length of 0.2-0.5 mu m, and has smaller agglomerated particle size of a short rod-shaped composite material, thereby preventing an ion channel from being blocked and enhancing the large-current charge and discharge capacity of the manganese-based oxide.
(3) The invention provides a preparation method of an organic matter/manganese-based oxide composite material, which is characterized in that an organic matter monomer is introduced into a hydrothermal kettle at high temperature and high pressure, and the intercalation of the organic matter in the manganese-based oxide is induced through the interaction between solvents, so that the interlayer spacing of the manganese-based oxide is increased, an ion channel is enlarged, and the activation process of the composite material is shortened; meanwhile, the length of the manganese-based oxide nanoneedle is shortened in the organic matter intercalation process, so that the ion migration path is shortened.
(4) The invention provides a preparation method of an organic matter/manganese-based oxide composite material, which is characterized in that the organic matter/manganese-based oxide composite material with a stable structure is obtained by regulating and controlling the temperature and time of hydrothermal reaction and the concentration of organic matter monomers, the composite process of manganese salt and organic matter monomers can be completed by only one-step hydrothermal reaction, the reaction temperature is low, the time is short, the operation is simple and easy, and high-temperature calcination is not needed.
(5) The invention provides an application of an organic matter/manganese-based oxide composite material, which is a zinc ion battery anode material; the composite material has excellent cycling stability and rate capability as a zinc ion battery anode material, and the reversible specific capacity of the organic matter/manganese-based oxide composite material under 0.2C can reach 168 mAh.g -1 Above, the composite showed 179mAh g as the rate was increased to 10C and returned to 0.2C -1 The above specific capacity does not cause structural collapse under heavy current charge and discharge.
Drawings
FIG. 1 is a scanning electron micrograph of a manganese-based oxide material of comparative example 1 and a p-phenylenediamine/manganese-based oxide composite material of example 1; wherein (a) and (b) are scanning electron micrographs of the manganese-based oxide material of comparative example 1; (c) and (d) is a scanning electron micrograph of the p-phenylenediamine/manganese-based oxide composite of example 1.
FIG. 2 is a cycle stability test of the manganese-based oxide material of comparative example 1 and the p-phenylenediamine/manganese-based oxide material of example 1; wherein (a) is a cycle stability test of the manganese-based oxide material of comparative example 1; (b) the cyclic stability test of the p-phenylenediamine/manganese-based oxide composite of example 1 was conducted.
FIG. 3 is a cycle stability test of the p-benzoquinone/manganese-based oxide composite material of example 2 and the methyl-p-benzoquinone/manganese-based oxide composite material of example 3; wherein (a) is the cycle stability test of the p-benzoquinone/manganese-based oxide composite material of example 2; (b) the cycle stability test of the methyl p-benzoquinone/manganese-based oxide composite material of example 3 was conducted.
FIG. 4 is a charge and discharge test curve of the manganese-based oxide material of comparative example 1 and the p-phenylenediamine/manganese-based oxide composite of example 1; wherein (a) is a charge and discharge test curve of the manganese-based oxide material of comparative example 1; (b) a charge and discharge test curve of the p-phenylenediamine/manganese-based oxide composite of example 1 is shown.
FIG. 5 is a rate capability test of a p-phenylenediamine/manganese-based oxide composite of example 1.
FIG. 6 is a rate capability test of the p-benzoquinone/manganese-based oxide composite material of example 2.
FIG. 7 is a rate capability test of the methyl p-benzoquinone/manganese-based oxide composite material of example 3.
Detailed Description
The invention is further illustrated by the following figures and detailed description, wherein the process is conventional unless otherwise specified, and the starting materials are commercially available from a public disclosure without further specification.
The following comparative examples and examples:
1. the electrochemical performance test method comprises the following steps:
(1) respectively mixing the manganese-based oxide material of comparative example 1 and the organic matter/manganese-based oxide composite materials 140mg, acetylene black 40mg and polyvinylidene fluoride 20mg of examples 1 to 3 according to a mass ratio of 7: 2: 1, mixing and grinding, namely adding polyvinylidene fluoride in a solution form, adding N-methyl pyrrolidone as a solvent and polyvinylidene fluoride as a solute, wherein the concentration of the polyvinylidene fluoride in the solution is 50mg/mL, the adding amount is 0.4mL, adding about 0.5mL of N-methyl pyrrolidone to form slurry, grinding for 15min, coating the slurry on a titanium foil, and drying in a 60-DEG C drying oven to obtain the zinc ion battery anode;
(2) and (3) cutting the positive electrode of the zinc ion battery obtained in the step (1) into a circular sheet electrode with the diameter of 11mm by using a cutting machine, matching with 100 mu m zinc foil, and assembling into a CR2032 type button cell for electrochemical test. The button cell structure is from bottom to top respectively: the device comprises a positive electrode shell, a gasket, a positive electrode, a glass fiber diaphragm, a zinc foil, a gasket, an elastic sheet and a negative electrode shell; before the button cell is assembled, 0.2mL of electrolyte is dripped into the button cell by a liquid-transfering gun; the solute of the electrolyte is ZnSO 4 And MnSO 4 The solvent is deionized water; in the electrolyte, ZnSO 4 And MnSO 4 The concentrations are respectively 2mol/L and 0.1 mol/L; after the battery is assembled, the battery is compacted by a battery packaging machine and subjected to electrochemical testing.
(3) Electrochemical test conditions
The cycle stability test is a constant current charge and discharge test, and the charge and discharge are continuously carried out for 130 circles under the charge and discharge multiplying power of 0.5C;
the rate performance test was continuous charging and discharging at charge and discharge rates of 0.2C, 0.5C, 1.0C, 2.0C, 3.0C, 5.0C, 8.0C, 10.0C, and 0.2C, in order.
2. Since the manganese-based oxide material prepared in comparative example 1 is different from the organic matter/manganese-based oxide composite material prepared in examples 1 to 3 only in that no organic matter is added, the mass fraction of organic matter in the organic matter/manganese-based oxide composite material prepared in examples 1 to 3 is calculated by the following formula:
organic mass fraction (mass of product from example-mass of corresponding product from comparative example)/mass of product from example × 100%.
Example 1
A preparation method of an organic matter/manganese-based oxide composite material comprises the following steps:
(1) 0.7785g of manganese acetate is dissolved in 48.4mL of deionized water, and the mixture is stirred until the manganese acetate is completely dissolved, so that a manganese acetate aqueous solution with the manganese acetate concentration of 92.96mmol/L is obtained; sequentially adding 1.6mL of 2mol/L sulfuric acid and 69.06mg of p-phenylenediamine powder into a manganese acetate aqueous solution, and continuously stirring for 20min to obtain a uniform clear solution A; the effect of adding 1.6mL of 2mol/L sulfuric acid and 69.06mg of p-phenylenediamine powder on the volume of the manganese acetate aqueous solution is ignored;
in the solution A, the concentration of sulfuric acid is 66 mmol/L;
in the solution A, the concentration of p-phenylenediamine powder is 13.2 mmol/L;
(2) 0.3696g of potassium permanganate is dissolved in 30mL of deionized water, and the potassium permanganate is stirred to be completely dissolved, so that a uniform potassium permanganate aqueous solution with the concentration of 78mmol/L is obtained; dropwise adding the aqueous potassium permanganate solution into the solution A obtained in the step (1) at the speed of 1.5mL/min by using a peristaltic pump under the stirring condition of the speed of 500r/min, wherein the volume ratio of the solution A obtained in the step (1) to the aqueous potassium permanganate solution is 1: 0.62; after the dropwise addition of the potassium permanganate solution is finished, continuously stirring for 30min at the speed of 500r/min to obtain a mixed solution B;
(3) transferring the mixed solution B obtained in the step (2) to a 100mL hydrothermal kettle, sealing, and then placing the hydrothermal kettle in an oven, wherein the hydrothermal reaction temperature is 130 ℃, and the reaction time is 16h, so as to obtain a solid-liquid mixture; after the hydrothermal reaction is finished, cooling the hydrothermal kettle, separating solid from a solid-liquid mixture, centrifugally cleaning the solid with deionized water, and drying the solid in an oven at 80 ℃ for 8 hours to obtain 0.5212g of the p-phenylenediamine/manganese-based oxide composite material, wherein the mass fraction of the p-phenylenediamine in the p-phenylenediamine/manganese-based oxide composite material is 3.40%.
Comparative example 1
Comparative example 1 on the basis of example 1 only, p-phenylenediamine was removed and the other steps and conditions were not changed to obtain 0.5035g of a manganese-based oxide material.
Example 2
A preparation method of an organic matter/manganese-based oxide composite material comprises the following steps:
(1) 0.6699g of manganese acetate is dissolved in 48.4mL of deionized water, and the mixture is stirred until the manganese acetate is completely dissolved, so that manganese acetate aqueous solution with the manganese acetate concentration of 80mmol/L is obtained; sequentially adding 1.6mL of 2mol/L sulfuric acid and 37.83mg of p-benzoquinone powder into a manganese acetate aqueous solution, and continuously stirring for 20min to obtain a uniform clear solution A; the effect of adding 1.6mL of 2mol/L sulfuric acid and 37.83mg of p-benzoquinone powder on the volume of the manganese acetate aqueous solution is ignored;
in the solution A, the concentration of sulfuric acid is 66 mmol/L;
in the solution A, the concentration of p-benzoquinone powder is 7.2 mmol/L;
(2) 0.2566g of potassium permanganate is dissolved in 25.7mL of deionized water, and the potassium permanganate is stirred to be completely dissolved, so that a uniform potassium permanganate aqueous solution with the concentration of 63.2mmol/L is obtained; dropwise adding the aqueous solution of potassium permanganate into the solution A obtained in the step (1) at the speed of 1mL/min by using a peristaltic pump under the stirring condition of the speed of 300r/min, wherein the volume ratio of the solution A obtained in the step (1) to the aqueous solution of potassium permanganate is 1: 0.53; after the dropwise addition of the potassium permanganate solution is finished, continuously stirring for 30min at the speed of 300r/min to obtain a mixed solution B;
(3) transferring the mixed solution B obtained in the step (2) to a 100mL hydrothermal kettle, sealing, and then placing the hydrothermal kettle in an oven, wherein the hydrothermal reaction temperature is 110 ℃, and the reaction time is 12h, so as to obtain a solid-liquid mixture; and after the hydrothermal reaction is finished, cooling the hydrothermal kettle, separating solid from a solid-liquid mixture, centrifugally cleaning the solid with deionized water, and drying the solid in an oven at 80 ℃ for 8 hours to obtain 0.4366g of the p-benzoquinone/manganese-based oxide composite material, wherein the mass fraction of the p-benzoquinone in the p-benzoquinone/manganese-based oxide composite material is 2.08%.
Comparative example 2
Comparative example 2 on the basis of example 2 only, p-benzoquinone was removed and the other steps and conditions were unchanged to obtain 0.4275g of manganese-based oxide material.
Example 3
A preparation method of an organic matter/manganese-based oxide composite material comprises the following steps:
(1) 0.8014g of manganese sulfate is dissolved in 48.25mL of deionized water, and the mixture is stirred until manganese acetate is completely dissolved, so that manganese acetate water solution with the manganese acetate concentration of 110mmol/L is obtained; sequentially adding 1.75mL of 2mol/L sulfuric acid and 85.48mg of methyl p-benzoquinone powder into a manganese acetate aqueous solution, and continuously stirring for 20min to obtain a uniform clear solution A; the influence of adding 1.75mL of 2mol/L sulfuric acid and 85.48mg of methyl p-benzoquinone powder on the volume of the manganese acetate aqueous solution is ignored;
in the solution A, the concentration of sulfuric acid is 73 mmol/L;
in the solution A, the concentration of p-benzoquinone powder is 14.5 mmol/L;
(2) dissolving 0.4935g of potassium permanganate in 32.33mL of deionized water, and stirring to completely dissolve the potassium permanganate to obtain a uniform potassium permanganate aqueous solution with the concentration of 96.6 mmol/L; dropwise adding the aqueous solution of potassium permanganate into the solution A obtained in the step (1) at the speed of 2mL/min by using a peristaltic pump under the stirring condition of the speed of 600r/min, wherein the volume ratio of the solution A obtained in the step (1) to the aqueous solution of potassium permanganate is 1: 0.67; after the dropwise addition of the potassium permanganate solution is finished, continuously stirring for 60min at the speed of 600r/min to obtain a mixed solution;
(3) transferring the mixed solution obtained in the step (2) to a 100mL hydrothermal kettle, sealing, and then placing the hydrothermal kettle in an oven, wherein the hydrothermal reaction temperature is 130 ℃, and the reaction time is 18h, so as to obtain a solid-liquid mixture; and after the hydrothermal reaction is finished, cooling the hydrothermal kettle, separating solid from the solid-liquid mixture, centrifugally cleaning the obtained solid with deionized water, and drying in an oven at 80 ℃ for 8 hours to obtain 0.5831g of the methyl-p-benzoquinone/manganese-based oxide composite material, wherein the mass fraction of the methyl-p-benzoquinone in the methyl-p-benzoquinone/manganese-based oxide composite material is 4.01%.
Comparative example 3
Comparative example 3 on the basis of example 3 only, methyl p-benzoquinone was removed and other steps and conditions were unchanged to obtain 0.5597g of manganese-based oxide material.
Scanning electron microscope characterization is carried out on the p-phenylenediamine/manganese-based oxide composite material prepared in the example 1 and the manganese-based oxide material prepared in the comparative example 1, and the results are shown in fig. 1, and when comparing (a) and (c) in fig. 1, the particle size of the manganese-based oxide aggregate is reduced after the p-phenylenediamine is added, the materials are more dispersed, and therefore the ion channel of the p-phenylenediamine/manganese-based oxide composite material is not easy to be blocked; comparing (b) and (d) in fig. 1, it can be seen that, after p-phenylenediamine is added, the length of the manganese-based oxide nanowire is shortened, and the obtained p-phenylenediamine/manganese-based oxide composite material mainly has a rod-like structure, the length is 0.3 μm to 0.5 μm, and compared with the manganese-based oxide material, the migration path of zinc ions is significantly shortened.
The characterization results of the scanning electron microscopes in the embodiments 2 and 3 are similar to those in the embodiment 1, and the obtained organic matter/manganese-based oxide composite material mainly has a rod-shaped structure, the length of the composite material is 0.3-0.5 μm, and compared with a manganese-based oxide material, the migration path of zinc ions is obviously shortened.
The p-phenylenediamine/manganese-based oxide composite material prepared in example 1 and the manganese-based oxide material prepared in comparative example 1 were subjected to a cycle stability test, and the results are shown in fig. 2, and it can be seen from (a) in fig. 2 that the initial specific capacity of the manganese-based oxide material at 0.5C is 58.96mAh g -1 After reaching the maximum specific capacity, the degradation occurred directly, and the stable maintenance cycle in the high capacity state was not possible, whereas the initial specific capacity at 0.5C of the p-phenylenediamine/manganese-based oxide composite according to (b) in FIG. 2 was 164.79mAh g -1 At 215.95mAh · g -1 The specific capacity state is kept for 50 circles, so that the p-phenylenediamine/manganese-based oxide composite material obtained after the p-phenylenediamine is added has higher initial specific capacity at 0.5 ℃, and can keep more circles at a high specific capacity state; the specific capacity of the p-phenylenediamine/manganese-based oxide composite material can reach 163 mAh.g at 130 circles -1 Higher than the specific capacity of the manganese-based oxide material of 114 mAh.g -1 The reason is that in the process of zinc ion intercalation and deintercalation, the interlayer p-phenylenediamine can play a supporting role, the structure of the p-phenylenediamine intercalated manganese-based oxide is more stable, and the capacity attenuation of the p-phenylenediamine/manganese-based oxide composite material is less along with the increase of the cycle number, which shows that the p-phenylenediamine molecule stably exists in the manganese-based oxide and does not dissolve and separate along with the increase of the use number.
The organic material/manganese-based oxide composite materials prepared in examples 2 and 3 were tested for cycle performance, and as a result, as shown in fig. 3 (a) and (b), respectively, the initial specific capacity of the p-benzoquinone/manganese-based oxide composite material prepared in example 2 at 0.5C was 132.82mAh g -1 At 205.59mAh · g -1 Keeping 55 circles under the specific capacity state; the initial specific capacity of the methyl p-benzoquinone/manganese-based oxide composite material prepared in example 3 at 0.5 ℃ is 147.29mAh g -1 At 196.94mAh · g -1 Compared with the comparative example 1, the composite materials prepared in the examples 2 and 3 have higher initial specific capacity at 0.5C, and can keep more turns in a high specific capacity state. The specific capacity of the p-benzoquinone/manganese-based oxide composite material obtained in the embodiment 2 at 130 circles can reach 154.46mAh g -1 The specific capacity of the methyl p-benzoquinone/manganese-based oxide composite material obtained in the embodiment 3 at 130 circles can reach 138.78mAh g -1 The specific capacity of the manganese-based oxide material is 114 mAh.g which are all higher than that of the manganese-based oxide material in comparative example 1 -1 The reason is that in the process of zinc ion intercalation and deintercalation, the interlaminar organic matter p-benzoquinone or methyl-p-benzoquinone can play a supporting role, the structure of the manganese-based oxide of the organic matter intercalation is more stable, and compared with the comparative example 1, the capacity attenuation of the composite materials prepared in the examples 2 and 3 is less along with the increase of the cycle number, which indicates that the organic matter p-benzoquinone or methyl-p-benzoquinone stably exists in the manganese-based oxide and is not dissolved and detached along with the increase of the use number.
The charge and discharge tests were performed on the p-phenylenediamine/manganese-based oxide composite material prepared in example 1 and the manganese-based oxide material prepared in comparative example 1, and the results are shown in fig. 4 (a) and (b), respectively: the first peripheral specific capacity of the composite material described in example 1 was 164.79mAh g -1 The first-cycle specific capacity of the manganese-based oxide material is obviously higher than that of the manganese-based oxide material in comparative example 1 by 58.96 mAh.g -1 The results show that the activity of the manganese-based oxide material after intercalation of organic p-phenylenediamine is improved, the specific capacity peak value can be reached only by less activation times, and the discharge curve still has the characteristics similar to the first cycle when 50 cycles are circulated, which shows that the structure of the composite material prepared in example 1 basically keeps stable, and no crystal phase or component transformation occurs.
The charge and discharge curves of the organic material/manganese-based oxide composite materials prepared in examples 2 and 3 were similar to those of example 1. Example 2 first-to-week ratio of the composite preparedThe capacity can reach 132.82mAh g -1 The first peripheral specific capacity of the composite material prepared in the embodiment 3 can reach 147.29mAh g -1 The first-cycle specific capacity of the manganese-based oxide material is obviously higher than that of the manganese-based oxide material in comparative example 1 by 58.96 mAh.g -1 It is shown that after the organic intercalation, the activity of the organic/manganese-based oxide composite material is improved, the specific capacity peak value can be reached only with less activation times, and the discharge curve still has the characteristics similar to the first cycle when the cycle is 50 cycles, which indicates that the composite material prepared in examples 2 and 3 basically keeps stable in structure and does not generate the transformation of crystalline phase or components.
The p-phenylenediamine/manganese-based oxide composite material prepared in example 1 was tested for rate capability and the results are shown in fig. 5, which shows that the p-phenylenediamine/manganese-based oxide composite material prepared in example 1 has excellent rate capability of 193mAh g at 0.2C -1 The material shows 207mAh g as the multiplying power is increased to 10C and then returns to 0.2C -1 The specific capacity of (a) indicates that the composite material does not collapse in structure due to large current charging and discharging.
The power performance test of the p-benzoquinone/manganese-based oxide composite material prepared in example 2 showed that the composite material had 168.02mAh g at 0.2C, as shown in FIG. 6 -1 The material showed 179.21mAh g as the rate was increased to 10C and returned to 0.2C -1 The specific capacity shows that the composite material does not collapse due to large-current charge and discharge and has excellent rate performance.
The results of the rate capability test of the methyl p-benzoquinone/manganese-based oxide composite material prepared in example 3 are shown in FIG. 7, and the composite material has 172.52mAh g at 0.2C -1 The material shows 188.63mAh g as the multiplying power is increased to 10C and then returns to 0.2C -1 The specific capacity shows that the composite material does not collapse due to large-current charge and discharge and has excellent rate performance.
Claims (9)
1. An organic/manganese-based oxide composite material, characterized in that: the composite material is prepared by compounding divalent manganese salt and an organic monomer by a hydrothermal method under the action of potassium permanganate; the divalent manganese salt is manganese acetate or manganese sulfate; the organic monomer is at least one of p-phenylenediamine, p-benzoquinone, methyl-p-benzoquinone and benzamide; based on the total mass of the organic matter/manganese-based oxide composite material as 100%, the mass fraction of the organic matter monomer is 1% -10%, and the mass fraction of the manganese-based oxide is 90% -99%.
2. The organic/manganese-based oxide composite material according to claim 1, wherein: the organic matter/manganese-based oxide is of a rod-shaped structure, and the length of the organic matter/manganese-based oxide is 0.2-0.5 mu m.
3. The organic/manganese-based oxide composite material according to claim 1 or 2, wherein: based on the total mass of the organic matter/manganese-based oxide composite material as 100%, the mass fraction of the organic matter monomer is 2% -4%, and the mass fraction of the manganese-based oxide is 96% -98%.
4. A method for preparing the organic/manganese-based oxide composite material according to any one of claims 1 to 3, wherein: the method comprises the following steps:
(1) sequentially adding a sulfuric acid solution and organic matter monomer powder into a divalent manganese salt aqueous solution, and stirring until a uniform and clear solution A is obtained;
in the divalent manganese salt aqueous solution, the concentration of divalent manganese salt is 80-110 mmol/L;
in the solution A, the concentration of sulfuric acid is 66-73 mmol/L;
in the solution A, the concentration of organic monomer powder is 7.2-14.5 mmol/L;
(2) dropwise adding a potassium permanganate aqueous solution with the concentration of 63.2-96.6 mmol/L into the solution A at the speed of 1-2 mL/min under the stirring condition at the speed of 300-600 r/min to obtain a mixed solution B;
the volume ratio of the solution A to the potassium permanganate aqueous solution is 1: 0.53 to 0.67;
(3) transferring the mixed solution B into a hydrothermal kettle, wherein the reaction temperature is 110-130 ℃, and the reaction time is 12-18 h; and (3) obtaining a solid-liquid mixture, and separating, washing and drying the obtained solid to obtain the organic matter/manganese-based oxide composite material.
5. The method for preparing an organic/manganese-based oxide composite material according to claim 4, wherein: and after the dropwise addition of the potassium permanganate solution is finished, continuously stirring the mixed solution B at the speed of 300-600 r/min for 30-60 min.
6. The method for preparing an organic/manganese-based oxide composite material according to claim 4, wherein: and centrifugally cleaning and drying the obtained solid in the solid-liquid mixture by using deionized water.
7. The method for preparing an organic/manganese-based oxide composite material according to claim 4, wherein: after the dropwise addition of the potassium permanganate solution is finished, continuously stirring the mixed solution B at the speed of 300-600 r/min for 30-60 min;
and centrifugally cleaning and drying the obtained solid in the solid-liquid mixture by using deionized water.
8. The use of the organic/manganese-based oxide composite material according to any one of claims 1 to 3, wherein: the application is a zinc ion battery anode material.
9. The use of an organic/manganese-based oxide composite material according to claim 8, wherein: the specific application method is as follows:
the organic matter/manganese-based oxide composite material, the conductive agent and the binder are mixed according to the mass ratio of (6.5-7): (2-3): (0.5-1) mixing and grinding, adding an organic solvent to form slurry, then coating the slurry on a current collector, and drying in a drying oven at the temperature of 60-80 ℃ to obtain the battery anode;
the conductive agent is acetylene black, carbon black, super P or carbon nano tube;
the binder is polyvinylidene fluoride or polytetrafluoroethylene;
the organic solvent is N-methyl pyrrolidone;
the current collector is a titanium foil or a stainless steel net.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210522048.3A CN115000363B (en) | 2022-05-13 | 2022-05-13 | Organic matter/manganese-based oxide composite material and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210522048.3A CN115000363B (en) | 2022-05-13 | 2022-05-13 | Organic matter/manganese-based oxide composite material and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115000363A true CN115000363A (en) | 2022-09-02 |
| CN115000363B CN115000363B (en) | 2023-11-14 |
Family
ID=83027513
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210522048.3A Active CN115000363B (en) | 2022-05-13 | 2022-05-13 | Organic matter/manganese-based oxide composite material and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115000363B (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105826088A (en) * | 2016-05-10 | 2016-08-03 | 复旦大学 | Carbon aerogel/manganese dioxide combined electrode material with multi-level structure, and preparation method thereof |
| CN111410232A (en) * | 2020-04-26 | 2020-07-14 | 张韩生 | Preparation method of manganese dioxide positive electrode material |
| CN113270577A (en) * | 2021-05-13 | 2021-08-17 | 苏州科技大学 | Aqueous zinc ion battery and positive electrode material |
| US20220037670A1 (en) * | 2019-04-15 | 2022-02-03 | Contemporary Amperex Technology Co., Limited | Positive electrode plate, electrochemical apparatus, and apparatus |
-
2022
- 2022-05-13 CN CN202210522048.3A patent/CN115000363B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105826088A (en) * | 2016-05-10 | 2016-08-03 | 复旦大学 | Carbon aerogel/manganese dioxide combined electrode material with multi-level structure, and preparation method thereof |
| US20220037670A1 (en) * | 2019-04-15 | 2022-02-03 | Contemporary Amperex Technology Co., Limited | Positive electrode plate, electrochemical apparatus, and apparatus |
| CN111410232A (en) * | 2020-04-26 | 2020-07-14 | 张韩生 | Preparation method of manganese dioxide positive electrode material |
| CN113270577A (en) * | 2021-05-13 | 2021-08-17 | 苏州科技大学 | Aqueous zinc ion battery and positive electrode material |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115000363B (en) | 2023-11-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111244448B (en) | In-situ carbon-coated high-rate large-size Prussian blue type sodium ion positive electrode material and preparation method thereof | |
| CN103474625B (en) | A kind of Olivine-type Cathode Material in Li-ion Batteries method for coating of nucleocapsid structure | |
| CN105226285B (en) | A kind of porous Si-C composite material and preparation method thereof | |
| CN103972497B (en) | Lithium ion battery Co2snO4/ C nano composite negative pole material and preparation and application thereof | |
| CN112151804A (en) | Prussian blue analogue-based carbon-coated transition metal oxide and preparation method and application thereof | |
| CN111403710B (en) | Aluminum trifluoride coated ternary doped lithium manganate cathode material and preparation method thereof | |
| CN107275590A (en) | A kind of porous Si-C composite material and its preparation method and application | |
| CN109980207B (en) | Lithium manganate lithium ion battery positive electrode material and preparation method and application thereof | |
| CN114784236B (en) | Coated Al and F co-doped monocrystalline lithium manganate positive electrode material and preparation method and application thereof | |
| CN114300658A (en) | Doped coated sodium-ion battery positive electrode material and preparation method thereof | |
| CN110336035B (en) | Tin dioxide/aluminum oxide doped carbon composite material and preparation method thereof | |
| CN113991089B (en) | Sodium ion battery and preparation method thereof | |
| CN111180704A (en) | Sodium-ion battery positive electrode material and preparation method and application thereof | |
| CN103187566B (en) | Tubular lithium-rich anode material, preparation method and application thereof | |
| CN112777611B (en) | Rhombohedral phase Prussian blue derivative and preparation method and application thereof | |
| CN104485450A (en) | Preparation method of lithium ion battery anode material FeV2O4 | |
| CN109659538B (en) | Preparation of rich lithium manganese-based oxide material based on coating of dopamine and lithium phosphate, product and application thereof | |
| CN115084471B (en) | Layered halide double perovskite lithium ion battery anode material and preparation method thereof | |
| CN110563052A (en) | preparation method of carbon and lanthanum oxide co-coated modified lithium nickel manganese oxide positive electrode material | |
| CN111313008B (en) | Magnesium-containing lithium-rich manganese-based positive electrode and preparation method thereof | |
| CN115000363B (en) | Organic matter/manganese-based oxide composite material and preparation method and application thereof | |
| CN115249792A (en) | Positive electrode lithium supplement material, preparation method thereof, positive plate and secondary battery | |
| CN114639827A (en) | Preparation method of iron-based fluoride composite positive electrode material | |
| CN112694132A (en) | ZnMn2O4Negative electrode material, preparation method and application thereof | |
| CN112909256A (en) | Perovskite type oxygen vacancy compound modified lithium-rich manganese-based positive electrode material, preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |