CN117832440A - Preparation method of carbon-coated positive electrode material, prepared carbon-coated positive electrode material and application of prepared carbon-coated positive electrode material - Google Patents
Preparation method of carbon-coated positive electrode material, prepared carbon-coated positive electrode material and application of prepared carbon-coated positive electrode material Download PDFInfo
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- 239000007774 positive electrode material Substances 0.000 title claims abstract description 64
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000002028 Biomass Substances 0.000 claims abstract description 88
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 64
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 60
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 59
- 238000002156 mixing Methods 0.000 claims abstract description 21
- 239000003960 organic solvent Substances 0.000 claims abstract description 18
- 150000001875 compounds Chemical class 0.000 claims abstract description 17
- 238000010438 heat treatment Methods 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 16
- 239000002994 raw material Substances 0.000 claims abstract description 14
- 238000010000 carbonizing Methods 0.000 claims abstract description 6
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 26
- 238000003756 stirring Methods 0.000 claims description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 13
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 229910001416 lithium ion Inorganic materials 0.000 claims description 13
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims description 10
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 239000011148 porous material Substances 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 6
- 235000017060 Arachis glabrata Nutrition 0.000 claims description 5
- 244000105624 Arachis hypogaea Species 0.000 claims description 5
- 235000010777 Arachis hypogaea Nutrition 0.000 claims description 5
- 235000018262 Arachis monticola Nutrition 0.000 claims description 5
- 239000003607 modifier Substances 0.000 claims description 5
- 235000020232 peanut Nutrition 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 4
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 claims description 4
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 4
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 4
- 229960002089 ferrous chloride Drugs 0.000 claims description 3
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 3
- 239000011790 ferrous sulphate Substances 0.000 claims description 3
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 3
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 3
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 3
- 235000020238 sunflower seed Nutrition 0.000 claims description 3
- 244000068988 Glycine max Species 0.000 claims description 2
- 235000010469 Glycine max Nutrition 0.000 claims description 2
- 229910018091 Li 2 S Inorganic materials 0.000 claims description 2
- 229910013684 LiClO 4 Inorganic materials 0.000 claims description 2
- PFYQFCKUASLJLL-UHFFFAOYSA-N [Co].[Ni].[Li] Chemical compound [Co].[Ni].[Li] PFYQFCKUASLJLL-UHFFFAOYSA-N 0.000 claims description 2
- HFCVPDYCRZVZDF-UHFFFAOYSA-N [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O Chemical compound [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O HFCVPDYCRZVZDF-UHFFFAOYSA-N 0.000 claims description 2
- 239000012298 atmosphere Substances 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 2
- 230000001681 protective effect Effects 0.000 claims description 2
- 229940079827 sodium hydrogen sulfite Drugs 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 5
- 229960001781 ferrous sulfate Drugs 0.000 claims 1
- 229960001516 silver nitrate Drugs 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 19
- 230000010287 polarization Effects 0.000 abstract description 9
- 239000010405 anode material Substances 0.000 abstract description 8
- 230000000052 comparative effect Effects 0.000 description 13
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- 239000002253 acid Substances 0.000 description 6
- 239000010406 cathode material Substances 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
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- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000009776 industrial production Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
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- 239000004289 sodium hydrogen sulphite Substances 0.000 description 2
- 239000006245 Carbon black Super-P Substances 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- 241000872198 Serjania polyphylla Species 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
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- WBHQBSYUUJJSRZ-UHFFFAOYSA-M sodium bisulfate Chemical compound [Na+].OS([O-])(=O)=O WBHQBSYUUJJSRZ-UHFFFAOYSA-M 0.000 description 1
- 229910000342 sodium bisulfate Inorganic materials 0.000 description 1
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- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention relates to the technical field of lithium battery material preparation, and discloses a preparation method of a carbon-coated positive electrode material, the prepared carbon-coated positive electrode material and application thereof, wherein the method comprises the following steps: (1) Carbonizing a biomass raw material to obtain a carbonized product, mixing the carbonized product with a structure regulator, and reacting at constant temperature to obtain a biomass carbon material; (2) Mixing the biomass carbon material with a lithium-containing compound and an organic solvent to obtain a lithium-rich biomass carbon material; (3) And mixing the lithium-rich biomass carbon material with a positive electrode material, and performing heat treatment to obtain the carbon-coated positive electrode material. According to the preparation method, the lithium-rich biomass carbon material is synthesized by the biomass carbon material and the lithium-containing compound, and the anode material is coated, so that the carbon-coated anode material is obtained, the overall conductivity of the material can be remarkably improved, and the polarization of a battery can be reduced.
Description
Technical Field
The invention relates to the technical field of lithium battery material preparation, in particular to a preparation method of a carbon-coated positive electrode material, the prepared carbon-coated positive electrode material and application thereof.
Background
The lithium ion battery is widely used because of its advantages of high voltage, high energy density, long life, high safety, etc. Meanwhile, the lithium ion battery system with high energy density generally has the problems of rapid capacity decay, serious battery polarization and the like, and greatly restricts the development speed of the lithium ion battery. Studies have shown that the use of suitable coatings is one of the effective methods to solve these problems.
The most common and widely used metal oxide coating, because of its stable nature and no participation in the reaction, can improve the stability of the electrode/electrolyte interface as a coating substance, thus improving the cycle performance and safety of the electrode, but has obvious drawbacks: lithium ion conductivity is poor. This will limit the rise in energy density and power density of lithium ion batteries.
Therefore, it is necessary to prepare a positive electrode material having both good lithium ion conductivity and stability.
Disclosure of Invention
The invention aims to solve the problems of poor structural stability and rapid capacity decay of a lithium ion battery positive electrode material in the prior art, and provides a preparation method of a carbon-coated positive electrode material, the prepared carbon-coated positive electrode material and application thereof.
In order to achieve the above object, a first aspect of the present invention provides a method for preparing a carbon-coated cathode material, wherein the method comprises the steps of:
(1) Carbonizing a biomass raw material to obtain a carbonized product, mixing the carbonized product with a structure regulator, and reacting at constant temperature to obtain a biomass carbon material;
(2) Mixing the biomass carbon material with a lithium-containing compound and an organic solvent to obtain a lithium-rich biomass carbon material;
(3) And mixing the lithium-rich biomass carbon material with a positive electrode material, and performing heat treatment to obtain the carbon-coated positive electrode material.
The second aspect of the invention provides a carbon-coated positive electrode material prepared by the preparation method of the first aspect.
The third aspect of the invention provides an application of the carbon-coated positive electrode material in the field of lithium ion batteries.
Through the technical scheme, the beneficial effects obtained are as follows:
(1) According to the invention, the nanoscale biomass carbon prepared from biomass raw materials is used as a matrix, so that the overall conductivity of the material can be remarkably improved, and the polarization of a battery can be reduced; the adopted lithium-rich component can quickly recover the capacity loss in the charge and discharge process, and the cycle life of the material is prolonged; the anode material obtained by coating has a stable structure, so that the damage to the material in the reaction process can be relieved, and the electrochemical performance of the anode material is obviously improved;
(2) In the invention, preferably, the organic solvent used in the preparation process can be recycled through recovery, which is beneficial to wide popularization in industrial production.
Drawings
FIG. 1 is a graph showing comparison of battery cycle results of the positive electrode materials prepared in examples 1 to 6 and comparative examples 1 to 2.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
The first aspect of the invention provides a preparation method of a carbon-coated positive electrode material, wherein the method comprises the following steps:
(1) Carbonizing a biomass raw material to obtain a carbonized product, mixing the carbonized product with a structure regulator, and reacting at constant temperature to obtain a biomass carbon material;
(2) Mixing the biomass carbon material with a lithium-containing compound and an organic solvent to obtain a lithium-rich biomass carbon material;
(3) And mixing the lithium-rich biomass carbon material with a positive electrode material, and performing heat treatment to obtain the carbon-coated positive electrode material.
According to the invention, the carbonized product obtained by carbonizing the biomass raw material is mixed with the structure regulator to obtain the biomass carbon material, and the biomass carbon material is further synthesized into the lithium-rich biomass carbon material with the lithium-containing compound, so that the anode material is coated, and the carbon-coated anode material is obtained, so that the overall conductivity of the material can be remarkably improved, and the polarization of a battery can be reduced.
According to the present invention, the kind and source of the biomass raw material are not particularly limited, and are materials capable of providing biomass carbon after carbonization, which are conventional in the art, and preferably, the biomass raw material is selected from at least one of peanut shell, sunflower seed shell, soybean shell and grain shell.
According to the invention, the biomass raw material is selected, the biomass carbon prepared by carbonizing the biomass raw material is used as a matrix, and the biomass carbon and the lithium-containing compound are synthesized into the composite coating material, so that the overall conductivity of the carbon-coated positive electrode material can be remarkably improved, the polarization of a battery is reduced, the raw material is easy to obtain, and the composite coating material is more suitable for large-scale industrial production.
According to the present invention, preferably, the mass ratio of the carbonized product to the structure modifier is 1:0.1-1, e.g. 1:0.1, 1:0.2, 1:0.3, 1:0.4, 1:0.5, 1:0.6, 1:0.7, 1:0.8, 1:0.9, 1:1, or any range therebetween, preferably 1:0.3-0.7. According to the invention, the mass ratio of the carbonized product to the structure regulator is controlled, the loose-structure biomass carbon material is prepared by the structure regulator, the structure of the biomass carbon material is easy to collapse due to excessive addition of the structure regulator, and the loose-structure biomass carbon material cannot be obtained due to insufficient addition of the structure regulator.
In the present invention, preferably, the carbonization process includes: and (3) carrying out constant-temperature acid cooking on the biomass raw material to obtain a carbonized product. According to a preferred embodiment of the invention, the carbonization process comprises: pulverizing biomass raw materials, decocting in concentrated sulfuric acid at constant temperature, filtering, washing to neutrality, and oven drying to obtain carbonized product.
In the present invention, the concentration of the concentrated sulfuric acid and the conditions of constant temperature acid boiling are not particularly limited, and the carbonization effect may be achieved. Preferably, the constant temperature acid cooking temperature is 40-120 ℃; the constant temperature acid boiling time is 0.5-2h. According to a preferred embodiment of the invention, the constant temperature acid cooking is followed by vacuum filtration. The conditions for washing and drying are not particularly limited, and may be conventional washing and drying conditions in the art.
According to the invention, preferably, the mixing in step (1) further comprises adding a solvent. The kind of the solvent is not particularly limited, but is preferably at least one selected from water, ethanol and methanol, and more preferably water.
According to the present invention, preferably, the mass ratio of the carbonized product and the solvent in the step (1) is 1:1-5, e.g., 1:1, 1:1.5, 1:2, 1:2.5, 1:3, 1:3.5, 1:4, 1:4.5, 1:5, or a range therebetween, preferably 1:2-4.
According to the present invention, preferably, the conditions of the isothermal reaction include: the reaction temperature is 25-100deg.C, such as 25deg.C, 30deg.C, 40deg.C, 50deg.C, 60deg.C, 70deg.C, 80deg.C, 90deg.C, 100deg.C, or any range therebetween, preferably 60-100deg.C; the reaction time is 1 to 24 hours, for example 1, 2, 3, 4, 6, 8, 10, 12, 14, 16, 18, 20, 22, 24 hours, or any range therebetween, preferably 6 to 18 hours. According to the invention, the constant-temperature reaction is carried out under the conditions, the porous biomass carbon material is prepared through the structure regulator, the reaction speed is too high to cause the collapse of the structure of the biomass carbon material, and the porous biomass carbon material cannot be obtained due to the too low reaction degree; too long reaction time leads to excessive reaction and easily causes structural damage of the biomass carbon material, and too short reaction is insufficient and the biomass carbon material with loose structure cannot be obtained.
According to the invention, preferably, the specific surface area of the biomass carbon material is more than or equal to 300m 2 /g, e.g. 300m 2 /g、350m 2 /g、400m 2 /g、450m 2 /g、500m 2 /g、550m 2 /g、600m 2 /g、650m 2 /g、700m 2 /g、750m 2 /g、800m 2 /g、850m 2 /g、900m 2 Per g, or any range therebetween, preferably 400-900m 2 /g。
According to the present invention, preferably, the biomass carbon material has a pore volume of 0.1 to 0.9cm 3 /g, e.g. 0.1cm 3 /g、0.2cm 3 /g、0.3cm 3 /g、0.4cm 3 /g、0.5cm 3 /g、0.6cm 3 /g、0.7cm 3 /g、0.8cm 3 /g、0.9cm 3 Per g, or any range therebetween, preferably 0.3-0.8cm 3 And/g. In the invention, the biomass carbon material has larger specific surface area and pore volume and has a loose structure.
In the invention, the specific surface area and the pore volume of the biomass carbon material are measured by a low-temperature nitrogen adsorption method.
According to the present invention, preferably, the structure modifier is selected from at least one of ammonium persulfate, sodium persulfate, potassium persulfate, sodium bisulfite, ferrous sulfate, ferrous chloride, and silver nitrate. According to the invention, the added structure regulator can be mixed with the carbonized product, and the structure of the carbonized product is regulated to obtain the loose biomass carbon material. According to a preferred embodiment of the present invention, the structure modifier is selected from at least two of ammonium persulfate, sodium persulfate, potassium persulfate, sodium bisulfite, ferrous sulfate, ferrous chloride, and silver nitrate.
According to the present invention, preferably, the structure-adjusting agent is ammonium persulfate and sodium bisulfite.
According to the present invention, preferably, the mass ratio of ammonium persulfate to sodium bisulfite is 1:0.1-2, e.g. 1:0.1, 1:0.2, 1:0.3, 1:0.4, 1:0.6, 1:0.8, 1:1. 1:1.2, 1:1.4, 1:1.6, 1:1.8, 1:2, or any range therebetween, preferably 1:0.3-1. According to the invention, the structure regulator is adopted to cooperate, so that the temperature required by the reaction can be reduced, and the reaction progress can be accelerated; excess ammonium persulfate can promote greater loosening of the material.
According to the present invention, the type and source of the lithium-containing compound are not particularly limited, and may be commercially available or may be prepared by an existing method, and may be capable of providing a lithium-rich component. Preferably, the lithium-containing compound is selected from CH 3 COOLi、Li 2 S、LiI、LiCl、LiClO 4 、LiClO 3 LiBr and LiBrO 3 At least one of them.
According to the present invention, the kind of the organic solvent is not particularly limited, and those skilled in the art can select an organic solvent conventional in the art. Preferably, the organic solvent is selected from at least one of methanol, ethanol, ethylene glycol and acetone.
In the present invention, the amount of the organic solvent is not particularly limited, and the biomass carbon material and the lithium-containing compound may be uniformly mixed by dissolving the lithium-containing compound. The organic solvent is adopted to dissolve the lithium-containing compound, the boiling point is relatively low, and the recycling of the organic solvent is easier to realize.
In the invention, the organic solvent is recovered by the special recovery device, so that the loss of the organic solvent can be reduced, and the cost can be reduced.
According to the invention, preferably the mass ratio of biomass carbon material to lithium containing compound is 1:0.05-1, e.g. 1:0.05, 1:0.1, 1:0.2, 1:0.3, 1:0.4, 1:0.5, 1:0.6, 1:0.8, 1:1, or any range therebetween, preferably 1:0.1-0.6.
According to the invention, preferably, the mixing in step (2) is carried out under stirring conditions, the stirring speed being in the range of 0.1-6m/s, for example 0.1m/s, 0.2m/s, 0.3m/s, 0.5m/s, 0.6m/s, 0.8m/s, 1m/s, 1.5m/s, 2m/s, 2.5m/s, 3m/s, 3.5m/s, 4m/s, 4.5m/s, 5m/s, 5.5m/s, 6m/s, or any two thereof, preferably 0.5-3m/s; the stirring time is 0.1 to 1h, for example 0.1h, 0.2h, 0.3h, 0.4h, 0.5h, 0.6h, 0.7h, 0.8h, 0.9h, 1h, or any range therebetween, preferably 0.1 to 0.6h.
In the invention, the stirring conditions are controlled within the range, so that the biomass carbon material and the lithium-containing compound are uniformly mixed, the biomass carbon material and the lithium-containing compound are easily combined unstably due to the too high stirring speed, the biomass carbon material is poor in dispersibility due to the too low stirring speed, and the uniformity of the lithium-rich biomass carbon material is influenced.
In the present invention, the stirring device is not particularly limited, and a person skilled in the art may select a conventional stirring device, and may realize a stirring effect.
According to a preferred embodiment of the present invention, the stirring in step (2) is performed by using a stirring paddle, and the stirring speed refers to the stirring speed of the outermost side when the stirring paddle is stirring, and the diameter of the stirring paddle is not particularly limited.
According to the present invention, preferably, in the step (3), the mass ratio of the lithium-rich biomass carbon material to the positive electrode material is 1:100-1000, e.g., 1:100, 1:150, 1:200, 1:250, 1:300, 1:350, 1:400, 1:450, 1:500, 1:550, 1:600, 1:650, 1:700, 1:750, 1:800, 1:850, 1:900, 1:1000, or a range therebetween, preferably 1:200-700.
According to the invention, the mass ratio of the lithium-rich biomass carbon material to the positive electrode material is limited to meet the above range, the lithium-rich biomass carbon material is uniformly coated on the surface of the positive electrode material, so that the leakage of the positive electrode material is avoided, the structural stability of the positive electrode material is improved, and the electrochemical performance of the positive electrode material is improved. The addition amount of the lithium-rich biomass carbon material is too small to realize the coating effect on the positive electrode material, and the electrode capacity of the positive electrode material after coating is reduced due to the excessive addition amount of the lithium-rich biomass carbon material.
According to the present invention, the kind and source of the positive electrode material are not particularly limited, and the positive electrode material is conventional in the art, and may be commercially available or may be prepared by an existing method. Preferably, the positive electrode material is a ternary positive electrode material, preferably nickel cobalt lithium manganate and/or nickel cobalt lithium aluminate.
According to the present invention, preferably, in the positive electrode material, the molar content of the metal element other than lithium is 100%, wherein the molar content of Ni is not less than 60%, preferably 60 to 95%. According to the method, the ternary positive electrode material is subjected to carbon coating, so that the overall conductivity of the material can be remarkably improved, and the polarization of a battery can be reduced; the unique lithium-rich component can quickly recover the capacity loss in the charge and discharge process and simultaneously prolong the cycle life of the material.
According to the present invention, preferably, the conditions of the heat treatment include: the heat treatment temperature is 200-700deg.C, such as 200deg.C, 250deg.C, 300 deg.C, 350deg.C, 400deg.C, 450deg.C, 500 deg.C, 550 deg.C, 600 deg.C, 650deg.C, 700 deg.C, or any range therebetween, preferably 350-550deg.C; the heat treatment time is 1 to 15 hours, for example 1, 2, 3, 4, 5, 6, 8, 10, 12, 15 or any range therebetween, preferably 5 to 10 hours, under a protective atmosphere. According to the invention, the conditions of heat treatment are controlled, so that the lithium-rich biomass carbon material and the anode material can be better combined while the material basic structure is not changed and the material performance is not reduced.
In the present invention, the heat treatment apparatus is not particularly limited, and a person skilled in the art can select a conventional heat treatment apparatus. According to a preferred embodiment of the invention, the heat treatment is carried out in a tube furnace.
The second aspect of the invention provides a carbon-coated positive electrode material prepared by the preparation method of the first aspect.
According to the carbon-coated positive electrode material prepared by the preparation method, the lithium-rich biomass carbon material is coated outside the positive electrode material, so that the overall conductivity of the material can be remarkably improved, the polarization of a battery can be reduced, and the specific lithium-rich component can be used for rapidly recovering the capacity loss in the charge and discharge process and prolonging the cycle life of the material. The carbon coating structure can relieve the damage to the positive electrode material in the reaction process, and the electrochemical performance of the positive electrode material is obviously improved.
The third aspect of the invention provides an application of the carbon-coated positive electrode material in the field of lithium ion batteries.
In the invention, the carbon-coated positive electrode material is applied to a lithium ion battery, and the lithium ion battery has higher cycle life and conductivity.
In the invention, the carbon-coated positive electrode material is prepared into the lithium ion battery, the existing preparation method can be adopted, and a specific preparation method can be reasonably selected by a person skilled in the art without the need of creative labor, and is not repeated herein.
The present invention will be described in detail below by way of examples and comparative examples. In the following examples and comparative examples, the reagents used in the present invention are commercially available unless otherwise specified.
Example 1
(1) Pulverizing peanut shell, decocting in 14mol/L concentrated sulfuric acid solution at 80deg.C for 1 hr, filtering with vacuum filter, washing to upper layer solution neutrality, oven drying to obtain carbonized product, sequentially adding 20g carbonized product, 6g ammonium persulfate and 4g sodium bisulphite into 60mL deionized water, reacting at 90deg.C for 13 hr, cooling, filtering, washing to upper layer solution neutrality, oven drying to obtain product with specific surface area of 700+ -50 m 2 Per gram, pore volume of 0.52.+ -. 0.05cm 3 A loose structure biomass carbon material per gram.
(2) The prepared 12g biomass carbon material was added to a solution in which 3.97g of Li was completely dissolved 2 Stirring for 0.3h in ethanol with the speed of 1m/S, and vacuum drying to obtain a lithium-rich biomass carbon material; and the organic solvent is recovered by a special device.
(3) Mixing 1g of the obtained lithium-rich biomass carbon material with 400g of LiNi 0.90 Co 0.06 Mn 0.04 O 2 After being uniformly mixed, the mixture is sintered for 8 hours at the constant temperature of 460 ℃ in a tubular furnace filled with Ar, and then the LiNi coated by the lithium-rich biomass carbon is obtained 0.90 Co 0.06 Mn 0.04 O 2 。
Example 2
(1) Pulverizing peanut shell, decocting in 14mol/L concentrated sulfuric acid solution at 80deg.C for 1 hr, filtering with vacuum filter, washing to upper layer solution neutrality, oven drying to obtain carbonized product, sequentially adding 20g carbonized product, 6g ammonium persulfate and 4g sodium bisulphite into 60mL deionized water, reacting at 90deg.C for 13 hr, cooling, filtering, washing to upper layer solution neutrality, oven drying to obtain product with specific surface area of 700+ -50 m 2 Per gram, pore volume of 0.52.+ -. 0.05cm 3 A loose structure biomass carbon material per gram.
(2) The prepared 12g biomass carbon material was added to a reactor in which 6.33g of CH was completely dissolved 3 Stirring for 0.3h in ethanol of COOLi at a speed of 1m/s, and vacuum drying to obtain a lithium-rich biomass carbon material; and the organic solvent is recovered by a special device.
(3) Mixing 1g of lithium-rich biomass carbon material with 400g of LiNi 0.90 Co 0.06 Mn 0.04 O 2 After being uniformly mixed, the mixture is sintered for 8 hours at the constant temperature of 460 ℃ in a tubular furnace filled with Ar, and then the LiNi coated by the lithium-rich biomass carbon is obtained 0.90 Co 0.06 Mn 0.04 O 2 。
Example 3
(1) Pulverizing sunflower seed shell, placing in 14mol/L concentrated sulfuric acid solution, decocting at 80deg.C for 1 hr, filtering with vacuum filter, washing to upper layer solution neutrality for multiple times, oven drying to obtain carbonized product, sequentially adding 20g carbonized product, 6g ammonium persulfate and 4g sodium bisulfate into 60mL deionized water, standing at 90deg.C for 13 hr, cooling, filtering, washing to upper layer solution neutrality, oven drying to obtain product with specific surface area of 660+ -50 m 2 Per gram, pore volume of 0.50.+ -. 0.05cm 3 A loose structure biomass carbon material per gram.
(2) The prepared 12g biomass carbon material was added to a solution in which 3.97g of Li was completely dissolved 2 Stirring for 0.3h in ethanol with the speed of 1m/S, and vacuum drying to obtain a lithium-rich biomass carbon material; and the organic solvent is recovered by a special device.
(3) Mixing 1g of lithium-rich biomass carbon material with 400g of LiNi 0.90 Co 0.06 Mn 0.04 O 2 After being uniformly mixed, the mixture is sintered for 8 hours at the constant temperature of 460 ℃ in a tubular furnace filled with Ar, and then the LiNi coated by the lithium-rich biomass carbon is obtained 0.90 Co 0.06 Mn 0.04 O 2 。
Example 4
A carbon-coated cathode material was prepared in the same manner as in example 1, except that ammonium persulfate was replaced with sodium persulfate of equal mass in step (1), and the other conditions were the same as in example 1.
Example 5
A carbon-coated cathode material was prepared in the same manner as in example 1 except that the mass of ammonium persulfate in step (1) was changed to 2g, and the mass of sodium hydrogensulfite was changed to 3g, under the same conditions as in example 1.
Example 6
A carbon-coated cathode material was prepared in the same manner as in example 1, except that the heat treatment time was 4.5 hours, the heat treatment temperature was 560℃and the other conditions were the same as in example 1.
Comparative example 1
Mixing 1g of carbon black with 400g of LiNi 0.90 Co 0.06 Mn 0.04 O 2 Uniformly mixing, and sintering for 8 hours at the constant temperature of 460 ℃ in a tubular furnace filled with Ar to obtain the conventional carbon-coated anode material.
Comparative example 2
A carbon-coated cathode material was prepared in the same manner as in example 1, except that in step (1), the peanut shells were crushed, placed in a 14mol/L concentrated sulfuric acid solution, and subjected to constant-temperature acid boiling at 80 ℃ for 1 hour, and then filtered by a vacuum suction filter, washed multiple times to the upper layer solution for neutrality, and dried to obtain a carbonized product. 12g of carbonized product was directly used for the synthesis of the lithium-rich biomass carbon material in step (2), otherwise the conditions were the same as in example 1.
Test case
The carbon-coated cathode materials prepared in the above examples and comparative examples, the binder polyvinylidene fluoride (PVDF) and the conductive agent conductive carbon black (Super-P) were weighed in a mass ratio of 96:2:2. This was poured into a 25mL weighing bottle, and an appropriate amount of dispersant N-methyl-2-pyrrolidone (NMP) was added dropwise. After being uniformly dispersed by a deaeration machine and the internal bubbles were discharged, the powder was uniformly coated on a clean aluminum foil current collector, and then placed in a vacuum drying oven at 120 ℃ for vacuum drying for 5 hours. And (3) compacting and shaping the dried pole piece by adopting a roller press, and punching the pole piece into a circular positive pole piece with the diameter of 12 mm. In a glove box protected by argon, the obtained round positive plate is taken as a positive electrode, a metal lithium plate is taken as a negative electrode, and 1mol/L LiPF is adopted 6 +ethylene carbonate/dimethyl carbonate/ethylmethyl carbonate (EC/DMC/EMC) as electrolyte, polypropylene/polyethylene/polypropylene (PP/PE/PP) composite membrane as separator, in order of assembly: positive electrode shell-positive electrode plate-electrolyte-diaphragm-lithium sheet-gasket-spring sheet-negative electrodeThe housing was assembled into a CR2032 coin cell.
The first-round charge-discharge curve at 0.2C was tested using a blue cell performance tester at a cutoff voltage ranging from 3.0 to 4.3V, and table 1 shows the buckling test results of examples 1 to 6 and comparative examples 1 to 2; the 1C cycle was tested and recorded for 50 cycles over the cut-off voltage range of 3.0-4.3V, with the capacity retention shown in figure 1. The activated cells were tested at a scan rate of 0.1mV/s using an electrochemical workstation in the range of 3.0-4.3V and the redox peaks of the cyclic voltammograms of examples 1-6 and comparative examples 1-2 were compared in Table 2.
TABLE 1
| Project | Gram capacity (mAh/g) | First effect (%) | 50 cycle retention (%) |
| Example 1 | 221.3 | 93.3 | 93.7 |
| Example 2 | 220.9 | 93.2 | 93.5 |
| Example 3 | 220.8 | 93.0 | 93.3 |
| Example 4 | 219.5 | 92.5 | 93.1 |
| Example 5 | 219.0 | 92.2 | 92.9 |
| Example 6 | 218.8 | 92.4 | 92.7 |
| Comparative example 1 | 215.6 | 90.6 | 90.8 |
| Comparative example 2 | 216.6 | 91.0 | 91.1 |
TABLE 2
Table 1 is a comparison of gram capacity and first effect results of the first charge and discharge of the batteries of the positive electrode materials prepared in examples 1 to 6 and comparative examples 1 to 2, and it can be seen from table 1 that the positive electrode materials of examples 1 to 6 coated with lithium-rich biomass carbon have relatively better first-round charge and discharge performance.
Fig. 1 is a comparison graph of battery cycle results for the positive electrode materials prepared in examples 1-6 and comparative examples 1-2, wherein the cycle life of the positive electrode materials coated with lithium-rich biomass carbon in examples 1-6 is significantly improved.
Table 2 shows that the oxidation-reduction peaks of the cyclic voltammograms at the same sweep rate are compared with those of the positive electrode material batteries prepared in examples 1-6 and comparative examples 1-2 after the positive electrode material batteries are activated, and as can be seen from Table 2, the positive electrode materials coated with lithium-rich biomass carbon prepared in examples 1-6 have higher oxidation peak intensities near 4.23V and reduction peak intensities near 4.10V, which indicates that the conductivity of the materials is better; the smaller the potential difference between the oxidation peak and the reduction peak, the smaller the polarization phenomenon of the material. Thus, it can be demonstrated that the positive electrode material coated with lithium-rich biomass carbon has better conductivity and a smaller degree of polarization. In addition, the organic solvent used in the preparation process can be easily recycled, and the method is more beneficial to popularization to industrial production.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (10)
1. A method for preparing a carbon-coated positive electrode material, comprising the steps of:
(1) Carbonizing a biomass raw material to obtain a carbonized product, mixing the carbonized product with a structure regulator, and reacting at constant temperature to obtain a biomass carbon material;
(2) Mixing the biomass carbon material with a lithium-containing compound and an organic solvent to obtain a lithium-rich biomass carbon material;
(3) And mixing the lithium-rich biomass carbon material with a positive electrode material, and performing heat treatment to obtain the carbon-coated positive electrode material.
2. The preparation method according to claim 1, wherein the mass ratio of the carbonized product to the structure modifier is 1:0.1-1, preferably 1:0.3-0.7;
preferably, the mixing in step (1) further comprises adding a solvent;
preferably, the mass ratio of the carbonized product to the solvent in step (1) is 1:1-5, preferably 1:2-4;
preferably, the conditions of the isothermal reaction include: the reaction temperature is 25-100 ℃, preferably 60-100 ℃; the reaction time is 1 to 24 hours, preferably 6 to 18 hours.
3. The production method according to claim 1 or 2, wherein the biomass raw material is selected from at least one of peanut shell, sunflower seed shell, soybean shell, and grain shell;
preferably, the specific surface area of the biomass carbon material is more than or equal to 300m 2 Preferably 400-900m 2 /g；
Preferably, the biomass carbon material has a pore volume of 0.1-0.9cm 3 Preferably 0.3-0.8 cm/g 3 /g。
4. The production method according to any one of claims 1 to 3, wherein the structure-adjusting agent is at least one selected from the group consisting of ammonium persulfate, sodium persulfate, potassium persulfate, sodium hydrogensulfite, ferrous sulfate, ferrous chloride, and silver nitrate;
preferably, the structure modifier is ammonium persulfate and sodium bisulfite;
preferably, the mass ratio of the ammonium persulfate to the sodium bisulfite is 1:0.1-2, preferably 1:0.3-1.
5. The production process according to any one of claims 1 to 4, wherein the lithium-containing compound is selected from CH 3 COOLi、Li 2 S、LiI、LiCl、LiClO 4 、LiClO 3 LiBr and LiBrO 3 At least one of (a) and (b);
preferably, the organic solvent is selected from at least one of methanol, ethanol, ethylene glycol and acetone;
preferably, the mass ratio of the biomass carbon material to the lithium-containing compound is 1:0.05-1, preferably 1:0.1-0.6.
6. The preparation method according to any one of claims 1 to 5, wherein the mixing in step (2) is performed under stirring conditions at a stirring speed of 0.1 to 6m/s, preferably 0.5 to 3m/s; the stirring time is 0.1-1h, preferably 0.1-0.6h.
7. The preparation method according to any one of claims 1 to 6, wherein in the step (3), the mass ratio of the lithium-rich biomass carbon material to the positive electrode material is 1:100-1000, preferably 1:200-700 parts;
preferably, the positive electrode material is a ternary positive electrode material, preferably nickel cobalt lithium manganate and/or nickel cobalt lithium aluminate;
preferably, in the positive electrode material, the molar content of the metal element other than lithium is 100%, wherein the molar content of Ni is not less than 60%, preferably 60 to 95%.
8. The production method according to any one of claims 1 to 7, wherein the conditions of the heat treatment include: under protective atmosphere, the heat treatment temperature is 200-700 ℃, preferably 350-550 ℃; the heat treatment time is 1-15 hours, preferably 5-10 hours.
9. A carbon-coated positive electrode material produced by the production method according to any one of claims 1 to 8.
10. Use of the carbon-coated positive electrode material of claim 9 in the field of lithium ion batteries.
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