CN116093325A - Method for synthesizing lithium supplementing material by converting lithium cobalt oxide, lithium supplementing material and modified lithium ion battery anode material - Google Patents
Method for synthesizing lithium supplementing material by converting lithium cobalt oxide, lithium supplementing material and modified lithium ion battery anode material Download PDFInfo
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- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 167
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 164
- 239000000463 material Substances 0.000 title claims abstract description 118
- 230000001502 supplementing effect Effects 0.000 title claims abstract description 114
- 238000000034 method Methods 0.000 title claims abstract description 68
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 title claims abstract description 53
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 title claims abstract description 53
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical class [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 239000010405 anode material Substances 0.000 title abstract description 9
- 230000002194 synthesizing effect Effects 0.000 title abstract description 6
- CKFRRHLHAJZIIN-UHFFFAOYSA-N cobalt lithium Chemical compound [Li].[Co] CKFRRHLHAJZIIN-UHFFFAOYSA-N 0.000 claims abstract description 55
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 47
- 239000010941 cobalt Substances 0.000 claims abstract description 47
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 46
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 42
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 40
- 238000002161 passivation Methods 0.000 claims abstract description 38
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- 239000000843 powder Substances 0.000 claims abstract description 33
- 239000007787 solid Substances 0.000 claims abstract description 32
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- 238000005253 cladding Methods 0.000 claims abstract description 13
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- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 12
- 239000011261 inert gas Substances 0.000 claims abstract description 7
- 230000005496 eutectics Effects 0.000 claims description 30
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 24
- 229910052760 oxygen Inorganic materials 0.000 claims description 24
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 23
- 239000001301 oxygen Substances 0.000 claims description 23
- 239000002699 waste material Substances 0.000 claims description 19
- 230000003647 oxidation Effects 0.000 claims description 18
- 238000007254 oxidation reaction Methods 0.000 claims description 18
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(2+);cobalt(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 claims description 14
- 239000011248 coating agent Substances 0.000 claims description 13
- 238000000576 coating method Methods 0.000 claims description 13
- 229910018068 Li 2 O Inorganic materials 0.000 claims description 9
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- 238000012545 processing Methods 0.000 claims description 8
- 229910018071 Li 2 O 2 Inorganic materials 0.000 claims description 7
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 7
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 6
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 6
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 6
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 claims description 6
- 229910001947 lithium oxide Inorganic materials 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 239000007774 positive electrode material Substances 0.000 claims description 6
- 238000000926 separation method Methods 0.000 claims description 6
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- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 claims description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 3
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- 150000001345 alkine derivatives Chemical class 0.000 claims description 3
- 229910021446 cobalt carbonate Inorganic materials 0.000 claims description 3
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 3
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 3
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 3
- 229910000428 cobalt oxide Inorganic materials 0.000 claims description 3
- ZOTKGJBKKKVBJZ-UHFFFAOYSA-L cobalt(2+);carbonate Chemical compound [Co+2].[O-]C([O-])=O ZOTKGJBKKKVBJZ-UHFFFAOYSA-L 0.000 claims description 3
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 claims description 3
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 3
- HPGPEWYJWRWDTP-UHFFFAOYSA-N lithium peroxide Chemical compound [Li+].[Li+].[O-][O-] HPGPEWYJWRWDTP-UHFFFAOYSA-N 0.000 claims description 3
- 239000011707 mineral Substances 0.000 claims description 3
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 14
- -1 lithium cobalt oxide hydrochloric acid Chemical compound 0.000 abstract description 7
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- 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
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
-
- 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
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- 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
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
-
- 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
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
-
- 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
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention belongs to the technical field of lithium supplementing materials, and discloses a method for synthesizing a lithium supplementing material by converting lithium cobalt oxide, the lithium supplementing material and a modified lithium ion battery anode material. The method for preparing the lithium supplementing material by converting the lithium cobalt oxide comprises the steps of dissolving a lithium cobalt oxide hydrochloric acid solution, and evaporating and crystallizing to obtain a solid-phase product; adjusting the molar ratio of lithium to cobalt in the solid phase product to obtain lithium cobalt mixed solid powder; and (3) placing the lithium cobalt mixed solid powder under the condition of vacuum degree of 0.001-10 Pa for high-temperature high-vacuum sintering, and then adopting mixed gas comprising gaseous hydrocarbon and inert gas for carbon cladding passivation to obtain the lithium supplementing material. The lithium supplementing material provided by the invention has high lithium supplementing capacity and good air stability, can be used for providing lithium ions lost in the battery charging process, and has a wide application prospect.
Description
Technical Field
The invention belongs to the technical field of lithium supplementing materials, and particularly relates to a method for synthesizing a lithium supplementing material by converting lithium cobalt metal oxide, the lithium supplementing material and a modified lithium ion battery anode material.
Background
Along with the industrialization of China and the adjustment of energy structures, the new energy field of the lithium ion battery enters a rapid development stage. However, the rapid development of the industry also brings about the problems of great amount of solid waste of the waste lithium ion batteries, urgent need of treatment and the like. The price of lithium metal rapidly rises, so that a large amount of lithium-containing solids have recovery value, meanwhile, cobalt metal has scarce domestic resources, the market price fluctuation is huge, and cobalt has greater toxicity in lithium electronic batteries compared with metals such as iron, aluminum, copper, nickel, manganese and the like, so that the environmental protection problem is increasingly prominent. Therefore, there is an urgent need for the development of a technique for synthesizing a high-value product by reprocessing waste lithium cobalt oxide and lithium cobalt-containing waste materials.
The recovery technology development of lithium battery solid waste has been carried out for nearly twenty years, and the preparation of lithium supplement additives from waste lithium cobaltate and waste materials containing lithium cobalt is a research hotspot in recent years. There are a number of methods in the prior art for preparing lithium supplement additives from waste lithium cobalt oxide and lithium cobalt-containing waste materials, such as MeOF and molten metal lithium which can be mixed and stirred under a protective gas atmosphere to perform full reaction 2 O is a lithium supplementing agent; or taking a composite of graphene and nano cobaltosic oxide as a raw material, adding lithium metal powder, mixing, and sintering to prepare a lithium supplementing agent; or LiF, fe powder and graphite powder are used as raw materials, and a ball milling conversion synthesis method is adopted to prepare a lithium supplementing agent; or under the vacuum condition, heating to enable molten lithium to permeate into the pores of the porous carbon material to prepare a lithium supplementing material; or uniformly mixing the lithium-containing compound, the metal catalyst, the inorganic nonmetallic reducing agent and the conductive agent, and preparing the lithium supplementing material through high-temperature treatment.
However, in the prior art, the method of ball milling conversion synthesis, metal lithium melting method, high-temperature sintering and the like are mostly adopted to prepare the lithium supplementing material, the purity of the obtained lithium supplementing material is low, the electrical property is poor, the method has the problems of long synthesis time, low efficiency, difficult amplified production, poor safety performance and the like, and the large-scale production cannot be realized, so that the recycling of solid wastes of lithium batteries cannot be truly realized, and the limitation is large.
Disclosure of Invention
The invention aims to provide a method for synthesizing a lithium supplementing material by converting lithium cobalt oxide, the lithium supplementing material and a modified lithium ion battery anode material, wherein the lithium supplementing material has high lithium supplementing capacity and high air stability.
In a first aspect, the method for preparing the lithium supplementing material by converting lithium cobalt oxide provided by the invention adopts the following technical scheme:
the method for preparing the lithium supplementing material by converting the lithium cobalt oxide comprises the steps of dissolving the lithium cobalt oxide by adopting a hydrochloric acid solution, and performing solid-liquid separation to obtain a liquid phase for evaporation crystallization to obtain a solid phase product; determining the content of lithium and cobalt in the solid-phase product, and adding a lithium source and/or a cobalt source to adjust the molar ratio of lithium to cobalt in the solid-phase product to obtain lithium cobalt mixed solid powder; and (3) placing the lithium cobalt mixed solid powder under the condition of vacuum degree of 0.001-10 Pa for high-temperature high-vacuum sintering, and then adopting mixed gas for carbon cladding passivation to obtain the lithium supplementing material, wherein the mixed gas comprises gaseous hydrocarbon and inert gas.
In some specific embodiments, the lithium cobalt oxide is selected from one or more of a mineral containing a lithium cobalt component, a lithium cobalt containing compound produced during lithium cobalt processing, waste materials in the production of lithium cobalt oxide positive electrodes, waste lithium cobalt oxide pole pieces produced during battery processing, and waste lithium cobalt oxide batteries.
In some specific embodiments, the lithium source is selected from one or more of lithium hydroxide, lithium carbonate, lithium nitrate, lithium chloride, lithium oxide, and lithium peroxide; the cobalt source is selected from one or more of cobalt hydroxide, cobalt carbonate, cobalt nitrate, cobalt chloride, cobalt oxide and cobaltosic oxide.
In some specific embodiments, the lithium cobalt mixed solid powder has a lithium cobalt molar ratio of (0.01 to 100): 1.
In some embodiments, the high temperature high vacuum sintering temperature is 700 to 1600 ℃.
In some specific embodiments, the gaseous hydrocarbon is selected from one or more of an alkane gas, an alkene gas, and an alkyne gas.
In some specific embodiments, the mode of carbon coating passivation is to introduce mixed gas into the system, control the initial temperature at 300-800 ℃, cool to 180-220 ℃ at the speed of 5-10 ℃/h, cool along with furnace, and control the vacuum degree of the whole carbon coating passivation at 10-100 kPa.
In some embodiments, the method further comprises subjecting the first eutectic obtained by high temperature high vacuum sintering to an oxygen oxidation treatment to obtain a second eutectic after high temperature high vacuum sintering and before carbon cladding passivation.
In some specific embodiments, the oxygen oxidation treatment mode is to introduce oxygen into the system, control the initial temperature at 400-700 ℃, cool to 180-220 ℃ at the speed of 50-100 ℃/h, cool along with the furnace, and control the vacuum degree of the whole oxygen oxidation treatment process at 10-100 kPa.
In a second aspect, the present application provides a lithium supplementing material that adopts the following technical scheme:
the lithium supplementing material obtained by the method for preparing the lithium supplementing material by converting the lithium cobalt oxide comprises the following steps of 2 O or Li 2 O 2 Is a main body frame, and cobalt is loaded on the main body frame.
In a third aspect, the present application provides a modified lithium ion battery positive electrode material, which adopts the following technical scheme:
a modified lithium ion battery anode material comprises an anode material and the lithium supplementing material.
The invention has the beneficial effects that:
(1) The key point of the invention is that the lithium cobalt oxide is sequentially subjected to hydrochloric acid solution purification, evaporation crystallization, high-temperature high-vacuum sintering and carbon coating passivation, wherein cobalt can be effectively inserted into a lithium oxide lattice by carrying out high-temperature high-vacuum sintering on lithium cobalt mixed solid powder, the impurity removal effect is good, the organic combination of other processing steps enables the finally obtained lithium supplementing material to have good structure and high purity, the buckling charging capacity of the lithium supplementing material is larger than 412.3mAh/g, the electric activity is high, the charging capacity attenuation rate after being placed in an environment with relative humidity of 20% for 24 hours can be as low as 28.4%, the lithium supplementing material has high lithium supplementing capacity and good air stability, and the lithium supplementing material can be used for providing lithium ions lost in the battery charging process and has wide application prospect;
(2) The invention also provides a scheme for preparing the lithium supplementing material by adding oxygen oxidation treatment between high-temperature high-vacuum sintering and carbon cladding passivation, and the lattice structure of the lithium supplementing material is improved by the oxygen oxidation treatment, so that the lithium supplementing material can generate irreversible phase change in the charge and discharge process, thereby providing a large amount of lithium ions and further improving the lithium supplementing capacity of the lithium supplementing material.
Drawings
Fig. 1 is an XRD diffractogram of the lithium supplementing material provided in example 6 of the present invention.
Detailed Description
Based on the deep understanding of the characteristics of lithium cobalt oxide, the inventor creatively adopts a vacuum purification technology through intensive and extensive research, carries out high-temperature high-vacuum sintering treatment on lithium cobalt mixed solid powder obtained through hydrochloric acid solution purification and evaporative crystallization, and carries out carbon coating passivation treatment by taking gaseous hydrocarbon as a carbon source in combination with a material surface passivation treatment technology to obtain the lithium supplementing material with high purity and high electric activity.
In the process of preparing the lithium supplementing material by adopting the method provided by the invention, cobalt can be effectively embedded into the lattice structure of the lithium supplementing material, and the prepared lithium supplementing material is Li 2 O@Co composite material. Compared with other metal elements, the cobalt-catalyzed electrochemical reaction can generate a large amount of lithium ions in the charging process of the lithium supplementing material, and meanwhile, the irreversible phase change occurs, so that the removed lithium ions cannot return to the lattice structure of the lithium supplementing material. Therefore, the lithium supplementing material has high charging capacitance and low discharging capacitance, is high in lithium supplementing capacity, has good air stability after being subjected to carbon coating passivation treatment, and can be used as a lithium supplementing material in a modified lithium ion battery positive electrode material.
Specifically, the method for preparing the lithium supplementing material by converting the lithium cobalt oxide comprises the steps of dissolving the lithium cobalt oxide by adopting a hydrochloric acid solution, and performing solid-liquid separation to obtain a liquid phase for evaporation crystallization to obtain a solid phase product; determining the content of lithium and cobalt in the solid-phase product, and adding a lithium source and/or a cobalt source to adjust the molar ratio of lithium to cobalt in the solid-phase product to obtain lithium cobalt mixed solid powder; and (3) placing the lithium cobalt mixed solid powder under the condition of vacuum degree of 0.001-10 Pa for high-temperature high-vacuum sintering, and then adopting mixed gas for carbon cladding passivation to obtain the lithium supplementing material, wherein the mixed gas comprises gaseous hydrocarbon and inert gas.
In the present invention, the lithium cobalt oxide may be one or more of, but not limited to, minerals containing lithium cobalt components, lithium cobalt compounds generated during lithium cobalt processing, waste materials generated during lithium cobalt oxide positive electrode production, waste lithium cobalt oxide pole pieces generated during battery processing, and waste lithium cobalt oxide batteries. The lithium cobalt-containing compound generated during the lithium cobalt processing process may be, but is not limited to, one or more of lithium cobalt-containing carbonate, lithium cobalt-containing hydroxide, lithium cobalt-containing halide, and lithium cobalt-containing sulfide. The waste lithium cobalt oxide battery can be one or more of a test battery or a 3C, vehicle-mounted field and obsolete lithium cobalt oxide battery after being used in the energy storage field.
In the present invention, lithium cobalt oxide is dissolved in a high concentration hydrochloric acid solution, and a small amount of insoluble matter is removed by a solid-liquid separation method such as centrifugation and filtration. In some embodiments, the concentration of the hydrochloric acid solution used is 9 to 12mol/L, more specifically, the concentration of the hydrochloric acid solution may be 9mol/L, 9.5mol/L, 10mol/L, 10.5mol/L, 11mol/L, 11.5mol/L, 12mol/L, or any value therebetween.
In the invention, a lithium source or a cobalt source is added to adjust the molar ratio of lithium to cobalt in a solid phase product to (0.01-100), 1, lithium cobalt mixed solid powder is obtained, and then in a lithium supplementing material obtained by high-temperature high-vacuum sintering and carbon coating passivation of the lithium cobalt mixed solid powder, cobalt can play an excellent catalytic effect, promote the generation of electrochemical reaction, and the electrochemical activity of the lithium supplementing material is high. The molar ratio of lithium to cobalt of the lithium cobalt mixed solid powder may specifically be 0.1:1, 0.8:1, 1.5:1, 15:1, 35:1, 40:1, 50:1, 62:1, 70:1, 80:1, 95:1, 100:1, or any value therebetween.
In some embodiments, the lithium source used in adjusting the lithium cobalt molar ratio of the solid phase product is a lithium element-containing compound, and may specifically be, but is not limited to, one or more of lithium hydroxide, lithium carbonate, lithium nitrate, lithium chloride, lithium oxide, and lithium peroxide; the cobalt source is a cobalt-containing compound, and may specifically be, but not limited to, one or more of cobalt hydroxide, cobalt carbonate, cobalt nitrate, cobalt chloride, cobalt oxide, and tricobalt tetraoxide.
In the invention, under the conditions that the temperature is 700-1600 ℃ and the vacuum degree is 0.001-10 Pa, the lithium cobalt mixed solid powder is sintered at high temperature and high vacuum, and under the synergistic effect of high temperature and high vacuum, the anion impurities are removed by evaporation, and Li is formed 2 O is a crystal phase structure of a main framework, and cobalt can be effectively embedded into Li 2 In the O lattice, a first eutectic is finally obtained. Preferably, when the high-temperature high-vacuum sintering temperature is 900-1400 ℃ and the vacuum degree is 0.01-1 Pa, the lithium supplementing material with higher purity and electrochemical activity can be prepared.
In some specific embodiments, the temperature of the high temperature high vacuum sintering may be 700 ℃, 725 ℃, 760 ℃, 800 ℃, 850 ℃, 900 ℃, 1000 ℃, 1150 ℃, 1240 ℃, 1380 ℃, 1400 ℃, 1500 ℃, 1600 ℃, or any value therebetween; the vacuum degree may be 0.001Pa, 0.01Pa, 0.05Pa, 0.10Pa, 0.20Pa, 0.50Pa, 0.70Pa, 1.0Pa, 1.5Pa, 2.0Pa, 5.0Pa, 7.0Pa, 9.0Pa, 10.0Pa, or any value therebetween.
According to the invention, after the first eutectic body obtained by high-temperature high-vacuum sintering is cooled to 300-800 ℃, mixed gas is introduced until the vacuum degree is 10-100 kPa for carbon cladding passivation, and the temperature is gradually reduced at a cooling speed of 5-10 ℃/h in the carbon cladding passivation process, so that the formation of a good lattice structure is facilitated, and when the temperature is reduced to 180-220 ℃, the material is naturally cooled along with a furnace, so that the lithium supplementing material is obtained.
In some embodiments, the initial temperature of the carbon-coated passivation may specifically be 300 ℃, 350 ℃, 400 ℃, 450 ℃, 500 ℃, 550 ℃, 600 ℃, 650 ℃, 700 ℃, 750 ℃, 800 ℃, or any value therebetween; the cooling rate may be specifically 5 ℃/h, 6 ℃/h, 7 ℃/h, 8 ℃/h, 9 ℃/h, 10 ℃/h or any value in between; the temperature before natural cooling along with the furnace can be 180 ℃, 185 ℃, 190 ℃, 195 ℃, 200 ℃, 205 ℃, 210 ℃, 215 ℃, 220 ℃ or any value between the two; the vacuum degree of the carbon-coated passivation may be specifically 10kPa, 20kPa, 30kPa, 40kPa, 50kPa, 60kPa, 70kPa, 80kPa, 90kPa, 100kPa or any value therebetween.
In some embodiments, the gaseous hydrocarbon is selected from one or more of an alkane gas, an alkene gas, and an alkyne gas, and may specifically be, but is not limited to, one or more of methane, ethane, butane, ethylene, butene, acetylene, and butyne. To better retain Li in carbon-coated passivation 2 The O lattice, the gaseous hydrocarbon is preferably one or more of ethylene, acetylene and butyne.
In some embodiments, the inert gas is selected from one or more of helium, neon, and argon.
In some embodiments, the concentration of gaseous hydrocarbon in the mixed gas is 20-50% (v/v), specifically may be 20% (v/v), 25% (v/v), 30% (v/v), 35% (v/v), 40% (v/v), 45% (v/v), 50% (v/v), 55% (v/v), 60% (v/v), or any value therebetween; the concentration of the inert gas is 50 to 80% (v/v), and specifically may be 50% (v/v), 55% (v/v), 60% (v/v), 65% (v/v), 70% (v/v), 75% (v/v), 80% (v/v), or any value therebetween.
In some embodiments, the vacuum level of the carbon-coated passivation may specifically be 10kPa, 15kPa, 25kPa, 50kPa, 75kPa, 80kPa, 90kPa, 100kPa or any value therebetween.
In some embodiments, the method for converting lithium cobalt oxide to prepare a lithium-supplemented material specifically comprises the steps of:
s1, dissolving the lithium cobalt oxide by adopting a hydrochloric acid solution with the concentration of 9-12 mol/L, and performing solid-liquid separation to obtain a liquid phase for evaporating and crystallizing to obtain a solid phase product;
s2, detecting the molar ratio of lithium to cobalt in the solid phase product, adding lithium carbonate or cobaltosic oxide, and adjusting the molar ratio of lithium to cobalt in the solid phase product to (0.01-100): 1 to obtain lithium cobalt mixed solid powder;
s3, sintering the lithium cobalt mixed solid powder at the temperature of 700-1600 ℃ and the vacuum degree of 0.001-10 Pa at high temperature and high vacuum to obtain Li 2 O is a first blend of the body frame;
s4, adjusting the temperature of the first eutectic body to 300-800 ℃, then introducing mixed gas until the vacuum degree is 10-100 kPa, cooling at a cooling speed of 5-10 ℃/h, carrying out carbon-coated passivation on the first eutectic body, and naturally cooling to room temperature after the temperature is reduced to be lower than 180-220 ℃ to obtain the lithium supplementing material.
In addition, the method for preparing the lithium supplementing material by converting the lithium cobalt oxide provided by the invention can also add an oxygen oxidation treatment step between high-temperature high-vacuum sintering and carbon cladding passivation, namely, after the high-temperature high-vacuum sintering and before the carbon cladding passivation, the first eutectic obtained by the high-temperature high-vacuum sintering is subjected to oxygen oxidation treatment to obtain Li 2 O 2 And finally, carrying out carbon coating passivation on the second co-fusion body by adopting the mixed gas to obtain the lithium supplementing material with the discharge capacity smaller than 0.9mAh/g, wherein the lithium supplementing material uses Li 2 O 2 As a main body frame, irreversible phase change occurs while a large amount of lithium ions are extracted, and the extracted lithium ions cannot be inserted normally, so that a large amount of lithium ions can be provided, and the lithium supplementing capacity is large.
In the invention, after the first eutectic body obtained by high-temperature high-vacuum sintering is cooled to 400-700 ℃, oxygen is introduced to the vacuum degree of 10-100 kPa for oxygen oxidation treatment, and the temperature is gradually reduced at the cooling speed of 50-100 ℃/h in the oxygen oxidation treatment process, thereby being beneficial to the formation of good lattice structure, and when the temperature is reduced to below 180-220 ℃, the second eutectic body is obtained by natural cooling along with a furnace.
In some embodiments, the oxygen oxidation treatment may specifically be initiated at a temperature of 400 ℃, 450 ℃, 500 ℃, 550 ℃, 600 ℃, 650 ℃, 700 ℃, or any value therebetween; the cooling rate may be specifically 50 ℃/h, 60 ℃/h, 75 ℃/h, 80 ℃/h, 85 ℃/h, 90 ℃/h, 95 ℃/h, 100 ℃/h or any value in between; the temperature before natural cooling along with the furnace can be 180 ℃, 185 ℃, 190 ℃, 195 ℃, 200 ℃, 205 ℃, 210 ℃, 215 ℃, 220 ℃ or any value between the two; the vacuum degree of the oxygen oxidation treatment may specifically be 10kPa, 15kPa, 30kPa, 45kPa, 50kPa, 80kPa, 100kPa or any value therebetween.
In the invention, the method for preparing the lithium supplementing material by converting the lithium cobalt oxide can specifically comprise the following steps:
s1, dissolving the lithium cobalt oxide by adopting a hydrochloric acid solution with the concentration of 9-12 mol/L, and performing solid-liquid separation to obtain a liquid phase for evaporating and crystallizing to obtain a solid phase product;
s2, detecting the molar ratio of lithium to cobalt in the solid phase product, adding lithium carbonate or cobaltosic oxide, and adjusting the molar ratio of lithium to cobalt in the solid phase product to (0.01-100): 1 to obtain lithium cobalt mixed solid powder;
s3, sintering the lithium cobalt mixed solid powder at the temperature of 700-1600 ℃ and the vacuum degree of 0.001-10 Pa at high temperature and high vacuum to obtain Li 2 O is a first blend of the body frame;
s4, adjusting the temperature of the first eutectic body to 400-700 ℃, then introducing oxygen to the vacuum degree of 10-100 kPa, cooling at the cooling speed of 50-100 ℃/h, carrying out oxygen oxidation treatment on the first eutectic body, and naturally cooling to room temperature after the temperature is reduced to be lower than 180-220 ℃ to obtain the product with the L i2 O 2 A second blend body that is a main body frame;
s5, adjusting the temperature of the second eutectic body to 300-800 ℃, then introducing mixed gas until the vacuum degree is 10-100 kPa, cooling at a cooling speed of 5-10 ℃/h, carrying out carbon-coated passivation on the second eutectic body, and naturally cooling to room temperature after the temperature is reduced to be lower than 180-220 ℃ to obtain the lithium supplementing material.
Second, the present application providesIs obtained by the method for preparing the lithium supplementing material by converting lithium cobalt oxide, which uses Li 2 O or Li 2 O 2 The lithium supplementing material has good electrochemical activity, high lithium supplementing capacity and high air stability.
Furthermore, the modified lithium ion battery anode material provided by the application comprises the anode material and the lithium supplementing material.
The following detailed description of embodiments of the invention is intended to be illustrative of the invention and is not to be taken as limiting the invention. The specific techniques or conditions are not identified in the examples and are performed according to techniques or conditions described in the literature in this field or according to the product specifications. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
Example 1.
The embodiment provides a preparation method of a lithium supplementing material, which takes lithium cobalt oxide (waste material in the production of lithium cobalt oxide anode) as a raw material, obtains lithium cobalt mixed solid powder through treatment, and obtains Li by high-temperature high-vacuum sintering 2 O is a first eutectic body of the main framework, and finally the lithium supplementing material is obtained through carbon cladding passivation, and the specific steps are as follows.
S1, dissolving lithium cobalt oxide by using a high-concentration hydrochloric acid solution with the concentration of 10mol/L, and filtering to remove a small amount of insoluble matters to obtain a lithium cobalt solution;
s2, evaporating and crystallizing the lithium cobalt solution to obtain a solid phase product, detecting the molar ratio of lithium to cobalt in the solid phase product, adding lithium carbonate or cobaltosic oxide, and adjusting the molar ratio of lithium to cobalt in the solid phase product to 2:1 to obtain lithium cobalt mixed solid powder;
s3, sintering the lithium cobalt mixed solid powder for 10 hours under high temperature and high vacuum under the conditions that the temperature is 950 ℃ and the vacuum degree is 0.3Pa, so as to remove the anion impurities by evaporation and obtain Li 2 O is a first blend of the body frame;
s4, cooling the first eutectic body to 500 ℃, then introducing mixed gas containing 40% (v/v) acetylene and 60% (v/v) argon to the vacuum degree of 50kPa, cooling at the cooling speed of 10 ℃/h to perform carbon-coated passivation on the first eutectic body, and naturally cooling to room temperature after the temperature is reduced to be lower than 200 ℃ to obtain the lithium supplementing material.
Examples 2 to 8.
Examples 2 to 8 lithium-compensating materials were prepared by the method provided in example 1, except that: the conditions for high-temperature high-vacuum sintering in step S3 were different depending on the molar ratio of lithium to cobalt in the lithium cobalt mixed solid powder, and the conditions were the same as in example 1, as shown in table 1.
Table 1.
FIG. 1 shows XRD diffraction patterns of a lithium-compensating material obtained by the method of example 6, wherein the prepared lithium-compensating material is Li 2 O@Co type lithium supplementing material prepared by using Li 2 O serves as a main body frame, and Co is loaded on the main body frame.
Comparative examples 1 to 7.
Comparative examples 1 to 7 lithium-compensating materials were prepared by the method provided in example 1, except that: the lithium cobalt mixed solid powder was treated in step S3 by high temperature sintering under normal pressure, the specific conditions are shown in table 2, and other conditions were the same as in example 1.
Table 2.
Test example 1.
The lithium-supplementing materials provided in examples 1 to 8 and comparative examples 1 to 7 were used as positive electrode materials, mixed with a conductive agent and a binder and press-molded to obtain positive electrodes, lithium metal sheets were used as negative electrodes in a mass ratio of 60:20:20, a button cell was prepared by a preparation method of a laboratory button cell CR2032, and electrochemical performance tests were performed, wherein the operating voltage ranges were set to 2.8 to 4.4V, CC at 0.05C/0.02C and DC at 0.05C during the test, and the test results are shown in Table 3.
Table 3.
As shown by test results, the lithium supplementing materials provided in examples 1-8 have a buckling charge capacity of 326.4-882.4 mAh/g, and have higher electrochemical activity than the lithium supplementing materials provided in comparative examples 1-7; and sintering the lithium cobalt mixed solid powder under the high-temperature and high-vacuum condition, so that cobalt can be effectively embedded into a crystal lattice of lithium oxide, and further a first eutectic body with a good structure is formed, and the lithium supplementing material can exert better electrical performance. The molar ratio of lithium to cobalt, the sintering temperature and the vacuum degree can all influence the electrical performance of the finally prepared lithium supplementing material; the impurities in the lithium cobalt mixed solid powder can be removed more thoroughly by increasing the temperature and reducing the vacuum degree, so that the prepared lithium supplementing material has higher purity and electrochemical activity.
Examples 9 to 14.
Examples 9-14 lithium-compensating materials were prepared according to the method provided in example 6, except that: the initial temperature of the carbon-coated passivation in step S4 was different, and the mixed gas used for the carbon-coated passivation of the first eutectic was different, as shown in table 4, and other conditions were the same as in example 6.
Table 4.
Comparative example 8.
This comparative example a lithium-compensating material was prepared according to the method provided in example 6, except that: the lithium supplementing material is obtained by high-temperature high-vacuum sintering, the treatment step of carbon cladding passivation is omitted, and other conditions are the same as those of the embodiment 6.
Test example 2.
In the test example, the air stability of the lithium supplementing materials provided in the examples 6, 9-14 and the comparative example 8 is tested, the charge capacity of the lithium supplementing materials before and after buckling in the environment with the relative humidity of 20% for 4 hours, 12 hours and 24 hours is detected, and the attenuation rate of the charge capacity is calculated; the test method of the snap-on charging capacity was the same as that of test example 1, and the results are shown in table 5.
Table 5.
As can be seen from the test results, the lithium supplementing materials provided in examples 6 and 9 to 14 were low in the rate of decay of the charge capacity after being left on shelf, compared with comparative example 8; according to the test results, the gaseous hydrocarbon is used as a carbon source, and the inert gas is matched to conduct carbon cladding passivation on the first eutectic body, so that the air stability of the lithium supplementing material can be improved, the lithium supplementing material can still keep good electrical performance in an environment with high humidity, and the lithium supplementing material has a wider application prospect. The gaseous hydrocarbon species used in the carbon-coated passivation process have a greater impact on the electrical properties and air stability of the lithium-compensating material. When acetylene is used as a carbon source to conduct carbon coating passivation on the first eutectic body, the structure of the first eutectic body can be well maintained, and the coating effect is good, so that the lithium supplementing material has high lithium supplementing capacity and excellent air stability.
Examples 15 to 18.
Examples 15 to 18 lithium-compensating materials were prepared by the method provided in example 6, except that: the lithium source and cobalt source used in the adjustment of the molar ratio of lithium to cobalt in the solid phase product in step S2 were different, and specifically, as shown in table 6, the other conditions were the same as in example 6.
Table 6.
| Group of | Lithium source | Cobalt source |
| Example 15 | Lithium carbonate | Cobalt carbonate |
| Example 16 | Lithium nitrate | Lithium cobalt oxide |
| Example 17 | Lithium chloride | Cobalt oxide |
| Example 18 | Lithium carbonate | Tricobalt tetraoxide |
Comparative examples 9 to 13.
Comparative examples 9 to 13 lithium-compensating materials were prepared according to the method provided in example 6, except that: the molar ratio of lithium non-cobalt metal in the solid phase product was adjusted using a lithium source and a non-cobalt metal source in step S2 using lithium non-cobalt metal oxide as a raw material, and specifically as shown in table 7, the other conditions were the same as in example 6.
Table 7.
Test example 3.
The charge and discharge capacities of the lithium supplement materials provided in examples 6 and 15 to 18 and comparative examples 9 to 13 were tested according to the test method provided in test example 1, and the test results are shown in table 8.
Table 8.
The test result shows that the lithium supplementing material prepared by using different additional lithium sources and cobalt sources to adjust and adjust the molar ratio of lithium to cobalt of the solid-phase product has high charging capacitance and good electrical property, namely the method for preparing the lithium supplementing material has low requirement on raw materials and high universality.
Meanwhile, as can be seen from comparison of the test results of the charge and discharge capacities of the lithium supplementing materials provided in comparative examples 9 to 13 and example 6, cobalt can be effectively intercalated into the crystal lattice of lithium oxide, so that electrochemical reaction occurring in the lithium supplementing material is better catalyzed, the occurrence of deep lithium removal process is facilitated, more lithium ions are provided, and the lithium supplementing material has higher lithium supplementing capacity.
Example 19.
The embodiment provides a preparation method of a lithium supplementing material, which takes lithium cobalt oxide (waste lithium cobalt oxide battery) as a raw material, obtains lithium cobalt mixed solid powder through treatment, and obtains Li through high-temperature high-vacuum sintering 2 O is a first eutectic body of a main framework, and then oxygen is introduced for oxidation to prepare Li 2 O 2 Is a second eutectic body of the main body frame, and is finally subjected to carbon coating passivation treatment to prepare the lithium supplementing agentThe materials and specific steps are shown below.
S1, dissolving lithium cobalt oxide by using a high-concentration hydrochloric acid solution with the concentration of 10mol/L, and filtering to remove a small amount of insoluble matters to prepare a lithium cobalt solution;
s2, evaporating and crystallizing the lithium cobalt solution to obtain a solid phase product, detecting the molar ratio of lithium to cobalt in the solid phase product, adding lithium carbonate or cobaltosic oxide, and adjusting the molar ratio of lithium to cobalt in the solid phase product to 1:1 to obtain lithium cobalt mixed solid powder;
s3, sintering the lithium cobalt mixed solid powder for 5 hours under high temperature and high vacuum under the conditions that the temperature is 1050 ℃ and the vacuum degree is 0.05Pa, so as to remove anion impurities by evaporation and obtain Li 2 O is a first blend of the body frame;
s4, adjusting the temperature of the first eutectic body to 650 ℃, then introducing oxygen to the vacuum degree of 50kPa, cooling the first eutectic body at a cooling speed of 60 ℃/h, performing oxygen oxidation treatment, and naturally cooling to room temperature after the temperature is reduced to be lower than 200 ℃ to obtain L i2 O 2 A second blend body that is a main body frame;
s5, adjusting the temperature of the second eutectic body to 500 ℃, then introducing mixed gas containing 40% (v/v) acetylene and 60% (v/v) argon to a vacuum degree of 50kPa, cooling at a cooling speed of 10 ℃/h, carrying out carbon-coated passivation on the second eutectic body, and naturally cooling to room temperature after the temperature is reduced to be lower than 200 ℃ to prepare the lithium supplementing material.
Examples 20 to 22.
Examples 20-22 lithium-compensating materials were prepared by the method provided in example 19, except that: the molar ratio of lithium and cobalt in the lithium cobalt mixed solid powder was varied, and the temperature and vacuum degree of high-temperature high-vacuum sintering in step S3 were varied, and as shown in table 9, other conditions were the same as in example 19.
Table 9.
Test example 4.
The charge capacitance and the discharge capacitance of the lithium supplement materials provided in example 6 and examples 19 to 22 were tested according to the test method provided in test example 1, and the test results are shown in table 10.
Table 10.
As is clear from the test results, in the methods provided in examples 19 to 22, the first eutectic body was subjected to oxygen oxidation treatment before the carbon-coated passivation was performed, and the finally prepared lithium-supplementing material was prepared by Li 2 O 2 As a main body framework, the lithium supplementing material has extremely low discharge capacity of only 0.2-0.9 mAh/g, which indicates that the lithium supplementing materials provided in examples 19-22 have irreversible phase change in the charge and discharge process, the removed lithium ions cannot be normally inserted, a large amount of lithium ions can be provided, the lithium supplementing material has high lithium supplementing capacity, can be used for providing lithium ions lost in the battery charging process, and has extremely excellent performance.
Although embodiments of the present invention have been shown and described above, it will be understood that the above embodiments are illustrative and not to be construed as limiting the invention, and that variations, modifications, alternatives, and variations may be made in the above embodiments by those skilled in the art without departing from the spirit and principles of the invention.
Claims (11)
1. A method for preparing a lithium supplementing material by converting lithium cobalt oxide is characterized by comprising the following steps of: the method comprises the steps of dissolving the lithium cobalt oxide by adopting a hydrochloric acid solution, and performing solid-liquid separation to obtain a liquid phase for evaporating and crystallizing to obtain a solid phase product; determining the content of lithium and cobalt in the solid-phase product, and adding a lithium source and/or a cobalt source to adjust the molar ratio of lithium to cobalt in the solid-phase product to obtain lithium cobalt mixed solid powder; and (3) placing the lithium cobalt mixed solid powder under the condition of vacuum degree of 0.001-10 Pa for high-temperature high-vacuum sintering, and then adopting mixed gas for carbon cladding passivation to obtain the lithium supplementing material, wherein the mixed gas comprises gaseous hydrocarbon and inert gas.
2. The method for preparing a lithium supplementing material by converting lithium cobalt oxide according to claim 1, wherein the method comprises the following steps: the lithium cobalt oxide is selected from one or more of minerals containing lithium cobalt components, lithium cobalt compounds generated in the lithium cobalt processing process, waste materials in the lithium cobalt oxide positive electrode production, waste lithium cobalt oxide pole pieces generated in the battery processing process and waste lithium cobalt oxide batteries.
3. The method for preparing a lithium supplementing material by converting lithium cobalt oxide according to claim 1, wherein the method comprises the following steps: the lithium source is selected from one or more of lithium hydroxide, lithium carbonate, lithium nitrate, lithium chloride, lithium oxide and lithium peroxide; the cobalt source is selected from one or more of cobalt hydroxide, cobalt carbonate, cobalt nitrate, cobalt chloride, cobalt oxide and cobaltosic oxide.
4. The method for preparing a lithium supplementing material by converting lithium cobalt oxide according to claim 1, wherein the method comprises the following steps: the molar ratio of lithium to cobalt of the lithium cobalt mixed solid powder is (0.01-100): 1.
5. The method for preparing a lithium supplementing material by converting lithium cobalt oxide according to claim 1, wherein the method comprises the following steps: the high-temperature high-vacuum sintering temperature is 700-1600 ℃.
6. The method for preparing a lithium supplementing material by converting lithium cobalt oxide according to claim 1, wherein the method comprises the following steps: the gaseous hydrocarbon is selected from one or more of an alkane gas, an alkene gas, and an alkyne gas.
7. The method for preparing a lithium supplementing material by converting lithium cobalt oxide according to claim 1, wherein the method comprises the following steps: the method of carbon coating passivation is to introduce mixed gas into the system, control the initial temperature at 300-800 ℃, cool to 180-220 ℃ at the speed of 5-10 ℃/h, cool along with furnace, and control the vacuum degree of the whole carbon coating passivation at 10-100 kPa.
8. The method for preparing a lithium supplementing material by converting lithium cobalt oxide according to claim 1, wherein the method comprises the following steps: the method further comprises the step of carrying out oxygen oxidation treatment on the first eutectic body obtained by high-temperature high-vacuum sintering after high-temperature high-vacuum sintering and before passivation of the carbon coating to obtain a second eutectic body.
9. The method for preparing a lithium supplementing material by converting lithium cobalt oxide according to claim 8, wherein: the oxygen oxidation treatment mode is to introduce oxygen into the system, control the initial temperature at 400-700 ℃, cool to 180-220 ℃ at the speed of 50-100 ℃/h, cool along with the furnace, and control the vacuum degree of the whole oxygen oxidation treatment process at 10-100 kPa.
10. A lithium supplementing material obtained by the method for producing a lithium supplementing material by converting lithium cobalt oxide according to any one of claims 1 to 9, characterized in that: the lithium supplementing material is Li 2 O or Li 2 O 2 Is a main body frame, and cobalt is loaded on the main body frame.
11. A modified lithium ion battery positive electrode material is characterized in that: the modified lithium ion battery positive electrode material comprises a positive electrode material and the lithium supplementing material of claim 10.
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