CN105206823A - Preparation method of lithium ion battery positive electrode material - Google Patents
Preparation method of lithium ion battery positive electrode material Download PDFInfo
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- CN105206823A CN105206823A CN201510654315.2A CN201510654315A CN105206823A CN 105206823 A CN105206823 A CN 105206823A CN 201510654315 A CN201510654315 A CN 201510654315A CN 105206823 A CN105206823 A CN 105206823A
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- lithium
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- ion batteries
- anode material
- salt
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- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 26
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 239000007774 positive electrode material Substances 0.000 title abstract 3
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 17
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 14
- 150000002696 manganese Chemical class 0.000 claims abstract description 12
- 150000002815 nickel Chemical class 0.000 claims abstract description 12
- 239000000758 substrate Substances 0.000 claims abstract description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000001301 oxygen Substances 0.000 claims abstract description 8
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 8
- 239000013077 target material Substances 0.000 claims abstract description 8
- 239000002994 raw material Substances 0.000 claims abstract description 7
- 238000000227 grinding Methods 0.000 claims abstract description 6
- 238000000137 annealing Methods 0.000 claims abstract description 5
- 239000000203 mixture Substances 0.000 claims abstract description 5
- 238000000498 ball milling Methods 0.000 claims abstract description 4
- 239000008367 deionised water Substances 0.000 claims abstract description 4
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 4
- 238000011065 in-situ storage Methods 0.000 claims abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000001035 drying Methods 0.000 claims abstract description 3
- 239000010405 anode material Substances 0.000 claims description 19
- 239000011572 manganese Substances 0.000 claims description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 10
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 9
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical group O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 6
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 3
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 3
- 229910001947 lithium oxide Inorganic materials 0.000 claims description 3
- 229940093474 manganese carbonate Drugs 0.000 claims description 3
- 235000006748 manganese carbonate Nutrition 0.000 claims description 3
- 239000011656 manganese carbonate Substances 0.000 claims description 3
- IPJKJLXEVHOKSE-UHFFFAOYSA-L manganese dihydroxide Chemical compound [OH-].[OH-].[Mn+2] IPJKJLXEVHOKSE-UHFFFAOYSA-L 0.000 claims description 3
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 claims description 3
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 claims description 3
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 3
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 claims description 3
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 claims description 3
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 claims description 3
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical group [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 3
- 229910001220 stainless steel Inorganic materials 0.000 claims description 3
- 239000010935 stainless steel Substances 0.000 claims description 3
- 238000005245 sintering Methods 0.000 abstract description 7
- 239000000463 material Substances 0.000 abstract description 6
- 239000011363 dried mixture Substances 0.000 abstract 1
- 238000004544 sputter deposition Methods 0.000 abstract 1
- 239000010408 film Substances 0.000 description 12
- 229910052744 lithium Inorganic materials 0.000 description 10
- 239000010409 thin film Substances 0.000 description 7
- 238000007599 discharging Methods 0.000 description 6
- 229910052748 manganese Inorganic materials 0.000 description 6
- 229910052759 nickel Inorganic materials 0.000 description 6
- 239000013078 crystal Substances 0.000 description 5
- 230000007547 defect Effects 0.000 description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000004549 pulsed laser deposition Methods 0.000 description 3
- 239000007772 electrode material Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000001755 magnetron sputter deposition Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/08—Oxides
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/3407—Cathode assembly for sputtering apparatus, e.g. Target
- C23C14/3414—Metallurgical or chemical aspects of target preparation, e.g. casting, powder metallurgy
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a preparation method of a lithium ion battery positive electrode material. The method comprises the following steps: (1) dissolving high-purity lithium salt, nickel salt and manganese salt in deionized water in proportion, performing ball milling for 8 to 10 hours, and drying, wherein the content of the lithium salt is higher than 40-60%; (2) grinding a dried mixture for 1 to 2 hours, and pre-burning the mixture for 20 to 30 hours at the temperature of 700 to 800 DEG C; (3) grinding the raw material processed in the step (2) for 1 to 2 hours, tabletting under 25 to 35 MPa, sintering the raw material in a muffle furnace for 12 to 24 hours at the temperature of 1000 to 1100 DEG C to obtain a compact target material; (4) placing the obtained target material in a vacuum chamber, focusing the laser on the target material by utilizing an excimer laser via a lens, and transmitting plasma generated by the laser sputtering of the target material outwards to a substrate; and (5) maintaining the temperature and oxygen pressure constant, and performing in-situ annealing for 1 to 3 hours to obtain a film product which can be used as the lithium ion battery positive electrode material. The positive material prepared in the method is high in crystallinity and high in specific capacity and large-current discharge capacity.
Description
Technical field
The present invention relates to a kind of preparation method of anode material for lithium-ion batteries.
Background technology
Micro cell has become an important technical field and application direction at present, and the specific capacity of micro cell, cycle life, discharge capability and fail safe etc. directly affect its performance and application.Solid-State Thin Film Li-Ion Batteries thickness can reach micron dimension, has the advantages such as safety non-pollution, height ratio capacity, high stability, large current discharging capability, becomes an important branch of micro cell, have important impact and application in actual production.
For film lithium ion battery, its positive electrode has crucial effect to cycle life, discharge capability and fail safe, and the positive electrode therefore how preparing premium properties is the key link promoting micro cell performance.
The method preparing film lithium ion battery anode material at present mainly comprises chemical meteorology deposition, magnetron sputtering, rotary coating and Gas Sensor Films Deposited by Pulsed Laser Deposition (PLD) etc., but, it is uncontrollable still to there is complicated process of preparation, the positive electrode film crystal formation thickness of preparation and uniformity in current preparation method, make the defects such as its key performance is not enough, and positive electrode type and crystal formation also cannot adapt to the needs of micro cell, have a strong impact on battery performance.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of anode material for lithium-ion batteries, it is by selecting the material of optimization and utilizing the preparation technology improved, prepare and there is height ratio capacity, the positive electrode of large current discharging capability, solves the defect of positive electrode performance deficiency of current anode material for lithium-ion batteries complicated process of preparation, preparation.
For achieving the above object, according to the present invention, a kind of preparation method of anode material for lithium-ion batteries is provided, comprises the steps:
(1) in proportion high-purity lithium salts, nickel salt, manganese salt are dissolved in deionized water, wherein high excessive 40%-60%, the ball milling 8-10 hour post-drying of lithium salts;
(2) by the mixture grinding 1-2 hour after oven dry, and at 700 DEG C-800 DEG C pre-burning 20-30 hour;
(3) raw material after step (2) process is ground 1-2 hour again, then at 25-35MPa lower sheeting, then in 1000 DEG C of-1100 DEG C of Muffle furnaces, sinter 12-24 hour, obtain dense target material;
(4) target obtained above is placed in vacuum chamber, utilizes excimer laser scioptics by Laser Focusing on target, the plasma that laser splash target produces outwards is emitted on substrate;
(5) keep temperature oxygen pressure constant, in-situ annealing 1-3 hour, namely the film product obtained can be used as anode material for lithium-ion batteries.
As improvement of the present invention, the concrete ratio of described lithium salts, nickel salt, manganese salt is preferably Li:Ni:Mn=(1.4-1.6): 0.5:1.5.
As a further improvement on the present invention, described laser frequency is 8-10Hz, energy density 2-3J/cm
2.
As a further improvement on the present invention, described oxygen pressure is 20-40Pa.
As improvement of the present invention, described substrate is stainless steel, and this substrate temperature is at 750 DEG C-800 DEG C.
As improvement of the present invention, lithium salts is lithium hydroxide, lithium carbonate, one or more in lithia.
As improvement of the present invention, described nickel salt is nickel oxide, nickel hydroxide, one or more in nickelous carbonate.
As improvement of the present invention, described manganese salt is manganese dioxide, manganous hydroxide, one or more in manganese carbonate.
In general, the above technical scheme conceived by the present invention compared with prior art, has following advantage:
(1) lithium salts high excessive 40%-60% is selected during raw material ratio, thus the defect that can compensate because of lithium volatilization generation in high temperature sintering and film-forming process, thus make good, the thickness of thin-film material Crystal type prepared even, make its excellent electrochemical performance.
(2) described target is prepared by traditional ceramics sintering process, for improving target quality, adopts long-time high temperature pre-burning and sintering method, is the chemical property avoiding lithium disappearance generation defect in sintering and plated film to affect battery.
(3) method of the present invention can be prepared and have height ratio capacity, the positive electrode of large current discharging capability, makes the battery assembled have very high specific capacity and large current discharging capability.
Accompanying drawing explanation
The X-ray diffraction (XRD) that Fig. 1 is the positive electrode target according to the excessive lithium of the height constructed by one embodiment of the invention is composed;
Fig. 2 is positive electrode in Fig. 1 plated film 1 hour X-ray diffraction (XRD) spectrum of positive electrode film after annealing in process at 750 DEG C;
Fig. 3 is for having the electrochemistry multiplying power test curve of the lithium ion battery according to the film positive electrode constructed by one embodiment of the invention.
Embodiment
In order to make object of the present invention, technical scheme and advantage clearly understand, below in conjunction with drawings and Examples, the present invention is further elaborated.Should be appreciated that specific embodiment described herein only in order to explain the present invention, be not intended to limit the present invention.
According to the preparation method of the anode material for lithium-ion batteries of a preferred embodiment of the invention, it specifically comprises the steps:
1) with high-purity lithium salts such as LiOHH
2o (preferred purity 99.9%), nickel salt is NiO (preferred purity 99.99%) such as, manganese salt such as MnO
2(preferred purity 99.9%) is raw material, takes a certain amount of above raw material, then put into ball grinder, add appropriate amount of deionized water according to Li, Ni, Mn mol ratio 1.5:0.5:1.5, and ball milling 8 hours is also dried.
In the present embodiment, preferred lithium salts, nickel salt and manganese salt are respectively LiOHH
2o, NiO and MnO
2such as, but be not limited to this in the present invention, the mixture of in fact general lithium salts, nickel salt and manganese salt or corresponding salt all can use, and lithium salts can be lithium hydroxide, lithium carbonate, one or more in lithia, nickel salt can be nickel oxide, nickel hydroxide, one or more in nickelous carbonate, manganese salt is manganese dioxide, manganous hydroxide, one or more in manganese carbonate.
In the present embodiment, preferred Li, Ni, Mn mol ratio is 1.5:0.5:1.5, but be in fact not limited to this in the present invention, in fact Li, Ni, Mn mol ratio can be other ratios, such as Li, Ni, Mn mol ratio is 1.4:0.5:1.5 in one embodiment, and in another embodiment, Li, Ni, Mn mol ratio is 1.6:0.5:1.5.In the present invention, Li, Ni, Mn mol ratio is preferably Li:Ni:Mn=(1.4-1.6): 0.5:1.5.
By high for lithium salts excessive 40-60%, can compensate because of the defect that lithium volatilization produces in high temperature sintering and PLD film-forming process, thus make that the thin-film material Crystal type prepared is good, thickness even, makes its excellent electrochemical performance.
2) again by mixture dry, be placed in mortar and grind 1-2 hour, then in Muffle furnace with the ramp to 750 DEG C of 5 DEG C/min, constant temperature pre-burning 20 hours, is down to room temperature.
In fact, in the present invention, in burn-in process, Muffle furnace thermostat temperature can within the scope of 700 DEG C-800 DEG C, burn-in time 20-30 hour, and Muffle furnace heating rate can at 3-10 DEG C/min.
3) by the sample grinding 0.5-1 hour after pre-burning, add suitable amount of adhesive, continue grinding after 0.5-1 hour, target is become at the pressure of 30MPa, with the ramp to 1000 DEG C of 5 DEG C/min in Muffle furnace, Isothermal sinter 12 hours, obtains dense target material.
As shown in Figure 1, XRD test result shows that target is the positive electrode of spinel structure, and its peak type is sharp-pointed, and back end is smooth, occurs without any impurity peaks, illustrates that the crystal formation of target is excellent.
In fact, in the present invention, target tableting pressure is not limited to above-mentioned value, can be such as 25-35Mpa, in addition, the temperature of Muffle furnace Isothermal sinter can within the scope of 1000 DEG C-1100 DEG C, sintering time at 12-24 hour, specifically can be selected according to actual conditions.
4) target of formation is put into vacuum chamber, utilize stainless steel substrate and target distance to be 4-5cm, with molecular pump, vacuum pump is extracted into 2 × 10
-3pa, after three oxygen cleanings, keep oxygen to press as 25Pa, substrate temperature rises to 750 DEG C.Open excimer laser (being preferably KrF excimer laser in one embodiment), preferably its frequency is 10Hz, and laser energy density is set to 2J/cm
2, adjustment convex lens make Laser Focusing at target material surface, and the plasma of generation is outwards emitted on substrate.
As shown in Figure 2, XRD test result shows that main peak (111) peak shape of thin-film material is sharp-pointed, and without any impurity peaks, illustrate that film crystalline substance is intact, crystallinity is high.
(5) maintenance temperature, oxygen press constant in-situ annealing 1-3 hour, form film, namely can be used as anode material for lithium-ion batteries.
The described positive electrode obtained is assembled into the film lithium ion battery of standard, it has excellent chemical property.
Fig. 3 is that battery is in 3.0-4.9V voltage range, with under 0.2C constant current charge, respectively with 0.2C, 0.5C, 1C, 2C, 5C, 10C, the discharge curve of 0.2C electric discharge, can see that the thin-film material specific discharge capacity prepared by 750 DEG C significantly increases, large current discharging capability significantly promotes, at 0.2C, 0.5C, when changing between 1C, at 750 DEG C there is the step strengthened in the thin-film electrode material discharge capacity of preparation successively, greatly be better than the thin-film electrode material prepared by 650 DEG C, and when changing between multiplying power from 1C to 10C, engender capacity attenuation by a small margin, finally when discharge-rate is restored to 0.2C, capacity significantly gos up to first run 0.2C discharge capacity level again, explanation membrane structure is stablized, possess stronger cyclic reversibility and large current discharging capability.
Those skilled in the art will readily understand; the foregoing is only preferred embodiment of the present invention; not in order to limit the present invention, all any amendments done within the spirit and principles in the present invention, equivalent replacement and improvement etc., all should be included within protection scope of the present invention.
Claims (9)
1. a preparation method for anode material for lithium-ion batteries, comprises the steps:
(1) in proportion high-purity lithium salts, nickel salt, manganese salt are dissolved in deionized water, wherein high excessive 40%-60%, the ball milling 8-10 hour post-drying of lithium salts;
(2) by the mixture grinding 1-2 hour after oven dry, and at 700 DEG C-800 DEG C pre-burning 20-30 hour;
(3) raw material after step (2) process is ground 1-2 hour again, then at 25-35MPa lower sheeting, then in 1000 DEG C of-1100 DEG C of Muffle furnaces, sinter 12-24 hour, obtain dense target material;
(4) target obtained above is placed in vacuum chamber, utilizes excimer laser scioptics by Laser Focusing on target, the plasma that laser splash target produces outwards is emitted on substrate;
(5) keep temperature oxygen pressure constant, in-situ annealing 1-3 hour, namely the film product obtained can be used as anode material for lithium-ion batteries.
2. the preparation method of a kind of anode material for lithium-ion batteries according to claim 1, wherein, the concrete ratio of described lithium salts, nickel salt, manganese salt is preferably Li:Ni:Mn=(1.4-1.6): 0.5:1.5.
3. the preparation method of a kind of anode material for lithium-ion batteries according to claim 1 and 2, wherein, the concrete ratio of described lithium salts, nickel salt, manganese salt is preferably Li:Ni:Mn=1.5:0.5:1.5.
4. the preparation method of a kind of anode material for lithium-ion batteries according to any one of claim 1-3, wherein, described laser frequency is 8-10Hz, and energy density is 2-3J/cm
2.
5. the preparation method of a kind of anode material for lithium-ion batteries according to any one of claim 1-3, wherein, described oxygen pressure is 20-40Pa.
6. the preparation method of a kind of anode material for lithium-ion batteries according to any one of claim 1-4, wherein, described substrate is stainless steel, and this substrate temperature of laser splash is at 750 DEG C-800 DEG C.
7. the preparation method of a kind of anode material for lithium-ion batteries according to any one of claim 1-5, wherein, lithium salts is lithium hydroxide, lithium carbonate, one or more in lithia.
8. the preparation method of a kind of anode material for lithium-ion batteries according to any one of claim 1-6, wherein, described nickel salt is nickel oxide, nickel hydroxide, one or more in nickelous carbonate.
9. the preparation method of a kind of anode material for lithium-ion batteries according to any one of claim 1-7, wherein, described manganese salt is manganese dioxide, manganous hydroxide, one or more in manganese carbonate.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108923019A (en) * | 2018-06-30 | 2018-11-30 | 宁波革创新材料科技有限公司 | The preparation method of anode material for lithium-ion batteries based on magnetically controlled sputter method |
| CN109659539A (en) * | 2018-12-20 | 2019-04-19 | 电子科技大学 | A method of based on In-situ reaction and being prepared by recombinant anode material of lithium battery |
| CN116914128A (en) * | 2023-09-14 | 2023-10-20 | 山东华太新能源电池有限公司 | High-voltage high-stability lithium cobalt oxide positive electrode material for marine environment and preparation method thereof |
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|---|---|---|---|---|
| CN103855378A (en) * | 2012-11-30 | 2014-06-11 | 夏晖 | Preparation of novel all-solid-state thin-film cathode used for lithium ion battery |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103855378A (en) * | 2012-11-30 | 2014-06-11 | 夏晖 | Preparation of novel all-solid-state thin-film cathode used for lithium ion battery |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108923019A (en) * | 2018-06-30 | 2018-11-30 | 宁波革创新材料科技有限公司 | The preparation method of anode material for lithium-ion batteries based on magnetically controlled sputter method |
| CN108923019B (en) * | 2018-06-30 | 2021-05-25 | 深圳市神火照明有限责任公司 | Preparation method of lithium ion battery anode material based on magnetron sputtering method |
| CN109659539A (en) * | 2018-12-20 | 2019-04-19 | 电子科技大学 | A method of based on In-situ reaction and being prepared by recombinant anode material of lithium battery |
| CN116914128A (en) * | 2023-09-14 | 2023-10-20 | 山东华太新能源电池有限公司 | High-voltage high-stability lithium cobalt oxide positive electrode material for marine environment and preparation method thereof |
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