CN108598460A - A kind of anode material of lithium battery and preparation method thereof - Google Patents
A kind of anode material of lithium battery and preparation method thereof Download PDFInfo
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- CN108598460A CN108598460A CN201810374447.3A CN201810374447A CN108598460A CN 108598460 A CN108598460 A CN 108598460A CN 201810374447 A CN201810374447 A CN 201810374447A CN 108598460 A CN108598460 A CN 108598460A
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- lithium
- anode material
- positive electrode
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- ion batteries
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- 239000010405 anode material Substances 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims description 20
- 229910052744 lithium Inorganic materials 0.000 title claims description 20
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 65
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 64
- 239000011572 manganese Substances 0.000 claims abstract description 55
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 48
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 21
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910003885 O2-aFa Inorganic materials 0.000 claims abstract description 10
- 239000000908 ammonium hydroxide Substances 0.000 claims abstract description 10
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims abstract description 9
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 claims abstract description 8
- 229910003684 NixCoyMnz Inorganic materials 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 239000000126 substance Substances 0.000 claims abstract description 5
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims abstract description 4
- 239000000203 mixture Substances 0.000 claims abstract description 4
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims abstract description 4
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims abstract description 4
- 238000003836 solid-state method Methods 0.000 claims abstract description 4
- 229940099596 manganese sulfate Drugs 0.000 claims abstract description 3
- 235000007079 manganese sulphate Nutrition 0.000 claims abstract description 3
- 239000011702 manganese sulphate Substances 0.000 claims abstract description 3
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims abstract description 3
- 238000010438 heat treatment Methods 0.000 claims description 34
- 239000002245 particle Substances 0.000 claims description 31
- 239000000243 solution Substances 0.000 claims description 21
- 239000013078 crystal Substances 0.000 claims description 18
- 239000012298 atmosphere Substances 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 13
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 12
- 229910052748 manganese Inorganic materials 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 9
- 239000002243 precursor Substances 0.000 claims description 7
- 150000001768 cations Chemical class 0.000 claims description 6
- 230000014759 maintenance of location Effects 0.000 claims description 6
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 229910021645 metal ion Inorganic materials 0.000 claims description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 2
- 238000004070 electrodeposition Methods 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 239000011737 fluorine Substances 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims 1
- 239000007789 gas Substances 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims 1
- 229910052708 sodium Inorganic materials 0.000 claims 1
- 239000011734 sodium Substances 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 7
- 239000000463 material Substances 0.000 abstract description 6
- 238000000975 co-precipitation Methods 0.000 abstract description 5
- 239000000843 powder Substances 0.000 abstract description 2
- 238000005245 sintering Methods 0.000 description 44
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 8
- 238000012360 testing method Methods 0.000 description 6
- 239000010406 cathode material Substances 0.000 description 5
- 239000010941 cobalt Substances 0.000 description 4
- 229910017052 cobalt Inorganic materials 0.000 description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 238000005253 cladding Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000010189 synthetic method Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 229910008080 Li-Ni-Co-Mn Inorganic materials 0.000 description 2
- 229910006461 Li—Ni—Co—Mn Inorganic materials 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000002738 chelating agent Substances 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 206010013786 Dry skin Diseases 0.000 description 1
- 229910021311 NaFeO2 Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- QSNQXZYQEIKDPU-UHFFFAOYSA-N [Li].[Fe] Chemical compound [Li].[Fe] QSNQXZYQEIKDPU-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000008236 heating water Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000037427 ion transport Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 229910000357 manganese(II) sulfate Inorganic materials 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
-
- 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
- H01M4/50—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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a kind of anode material for lithium-ion batteries and preparation method thereof, including step 1, using nickel sulfate, cobaltous sulfate, manganese sulfate, sodium hydroxide, ammonium hydroxide as raw material, prepare spherical presoma using coprecipitation, chemical formula is (NixCoyMnz)(OH)2, wherein 0.1≤x≤0.2,0.1≤y≤0.2, x+y+z=1；Step 2 is first heated the presoma in step 15 hours with lithium hydroxide powder using high temperature solid-state method at 400 500 DEG C after evenly mixing；It mixes with lithium fluoride, is sintered 10 20 hours under the conditions of 750 1000 DEG C of mixture again, that is, anode material for lithium-ion batteries is prepared, chemical formula is Li [Li0.20Ni0.8xCo0.8yMn0.8z]O2‑aFa, wherein 0.1≤x≤0.2,0.1≤y≤0.2, x+y+z=1,0.002≤a≤0.02；The present invention also provides a kind of lithium ion batteries prepared using above-mentioned positive electrode.Anode material for lithium-ion batteries preparation process is simple in the present invention, and cost of material is low, and energy density is high, remarkable with performance of lithium ion battery prepared by this positive electrode.
Description
Technical field
The invention belongs to anode material for lithium-ion batteries to research and develop field, and in particular to a kind of anode material of lithium battery and
Preparation method.
Background technology
Occurs increasingly serious energy and environmental problem in global range, the increasingly scarcity of traditional fossil energy accelerates
Research of the people to high performance energy memory device, lithium ion battery is because it is high with energy density, service life is long, to environment
The advantages of close friend etc. and be widely used.In the construction of lithium ion battery, positive electrode determines entire lithium-ion electric
The total capacity in pond is the very crux in lithium ion battery evolution.Commercialization positive electrode is mostly cobalt acid lithium, phosphoric acid at present
Iron lithium, nickel-cobalt-manganternary ternary anode material etc. substantially increase the demand of raw material with the maturing of lithium ion battery technology
Adding, the requirement to energy density is also higher and higher, and the price of cobalt acid lithium and common nickel-cobalt-manganternary ternary anode material constantly increases,
The promotion of energy density is limited, and inexpensive in recent years, high-energy density lithium-rich manganese-based electrode material becomes the hot spot of research.
Li-Ni-Co-Mn systems layered cathode material has higher theoretical specific capacity compared to traditional positive electrode,
The channel of layer structure lithium ion transmission is the planar channel of entire lithium ion layer, to have faster lithium ion transport
Speed has better performance under larger electric current, while also having higher cycle performance.In addition, Li-Ni-Co-Mn systems
Layered cathode material uses manganese, nickel element, cheap, green non-poisonous using cobalt element, so the system positive electrode is to ring
Border is friendly, and cost is relatively low.
Coprecipitation is a kind of practical approach of common fairly large production electrode material in industrial production, compared to solid phase
Method has prodigious excellent although coprecipitation cost is higher in the control of material particle size and the purity of material
Gesture.It is such as entitled application No. is 201610284398.5《A kind of synthetic method of high-performance lithium-rich manganese-based anode material》Middle promulgated by the State Council
Bright patent provides a kind of synthetic method of high-performance lithium-rich manganese-based anode material：Co deposited synthesis is used first
Ni0.19Co0.13Mn0.68(OH)2Presoma；Then by presoma and LiOHH2O mixed sinterings obtain
Li1.2Ni0.15Co0.10Mn0.55O2；Finally by Al (NO3)3·9H2O is added in ethanol solution, adds certain mass
Li1.2Ni0.15Co0.10Mn0.55O2, stirring a period of time, add certain density LiOHH2O, adjusts pH, and heating water bath is done
Dry, sintering finally obtains the high-performance lithium-rich manganese-based anode material after synthesis nano aluminium oxide cladding.It is above-mentioned lithium-rich manganese-based
Positive electrode need to prepare nano aluminium oxide clad, and preparation process is complex.
Invention content
In order to solve the deficiencies in the prior art, the invention of this reality provides a kind of anode material for lithium-ion batteries, chemistry
Formula is Li [Li0.20Ni0.8xCo0.8yMn0.8z]O2-aFa；The present invention also provides the preparation sides of above-mentioned anode material for lithium-ion batteries
Method and a kind of lithium ion battery of application positive electrode preparation.Anode material for lithium-ion batteries preparation process letter of the present invention
Single, cost of material is low, and energy density is high, remarkable with performance of lithium ion battery prepared by this positive electrode.
Institute of the invention technique effect to be achieved is realized by following scheme：
The anode material for lithium-ion batteries provided in the present invention, chemical formula are Li [Li0.20Ni0.8xCo0.8yMn0.8z]O2-aFa,
In, 0.1≤x≤0.2,0.1≤y≤0.2, x+y+z=1,0.002≤a≤0.02.
Further, the lithium ion anode material is layered crystal structure；The positive electrode average diameter of particles is
4-6μm；The positive electrode particle compacted density is 1.40-1.60g/cm3.Above-mentioned positive electrode particle size distribution is uniform,
The compacted density of positive electrode particle can be effectively improved；In lithium ion battery manufacturing process, compacted density is to cell performance
Can there are large effect, suitable compacted density that can increase the discharge capacity of battery, reduce internal resistance, reduce polarization loss, prolong
The cycle life of long battery improves the utilization rate of lithium ion battery.Above-mentioned positive electrode particle compacted density is 1.40-1.60g/
cm3, the problem of having taken into account battery capacity, circulating battery and battery utilization rate.
A kind of preparation method of anode material for lithium-ion batteries is additionally provided in the present invention：Ball is first prepared using co-electrodeposition method
Shape (NixCoyMnz)(OH)2Presoma, then the lithium-rich manganese-based anode material Li for adulterating fluorine element is prepared using high temperature solid-state method
[Li0.20Ni0.8xCo0.8yMn0.8z]O2-aFa。
Further, the preparation method of the anode material for lithium-ion batteries, includes the following steps：
S01, spherical (NixCoyMnz)(OH)2The preparation of presoma：
Nickel sulfate, cobaltous sulfate, manganese sulfate are pressed into cation mole concentration ratio Ni2+:Co2+:Mn2+=x:y:Z is made into aqueous solution, wherein
0.1≤x≤0.2,0.1≤y≤0.2, x+y+z=1 set the concentration summation of all cations as 2.0mol/L；
By above-mentioned solution agitating and heating in an inert atmosphere, while sodium hydroxide solution and ammonium hydroxide are instilled, control reaction system pH
It is worth ranging from 10-11.5, spherical (Ni is made in filtration drying after the reaction was completexCoyMnz)(OH)2Granular precursor, wherein 0.1
≤ x≤0.2,0.1≤y≤0.2, x+y+z=1；
S02, layered crystal structure Li [Li0.20Ni0.8xCo0.8yMn0.8z]O2-aFaPreparation：
Granular precursor made from S01 is mixed with lithium hydroxide, metal ion summation and lithium ion rubs wherein in presoma
You are than being (0.6-0.8): (1.0-1.5)；
Said mixture is heated into 5h for 400-500 DEG C in atmosphere furnace, lithium fluoride is then mixed into and continues to be sintered at 750-1000 DEG C
Layered crystal structure Li [Li are made in 10-20h0.20Ni0.8xCo0.8yMn0.8z]O2-aFaParticle, wherein 0.1≤x≤0.2,0.1≤y
≤ 0.2, x+y+z=1.
Manganese is a kind of relatively cheap metal, and the cost of raw material is greatly lowered using manganese as raw material；It is main in the present invention
To include that aqueous solution co-deposition and high temperature sintering technique were prepared currently, co-precipitation and high temperature sintering are very ripe technique
Journey is simple.
Further, inert atmosphere described in S01 is nitrogen atmosphere；Atmosphere is air atmosphere in atmosphere furnace described in S02.
Reaction condition readily satisfies in preparation process, and nitrogen is cheap and easily-available inert gas, and environmentally friendly, in nitrogen atmosphere
In prepare presoma, prevent the pollution of extraneous element and the oxidation of ion；Air atmosphere is selected in S02, further reduced system
Standby cost.
Further, mixing speed described in S01 is 900-1100r/min；Heating temperature described in S01 is 500-600
℃.The stirred slow hybrid reaction being unfavorable between solution, stirring is too fast to be difficult to form precipitate nucleation, is unfavorable for granular precursor
Generation and deposition.
Further, concentration of sodium hydroxide solution described in S01 is 2.0mol/L；The ammonia concn is 4.0mol/L.
Further, ammonium hydroxide described in S01 is used for doing chelating agent, is not expendable raw material；During the ammonium hydroxide instills
Control NH4 +A concentration of 0.30-0.36mol/L in reaction solution.
Further, (Ni obtained in S01xCoyMnz)(OH)2A diameter of 4-6 μm of granular precursor.
A kind of lithium ion battery using above-mentioned material as positive electrode, the lithium-ion electric are additionally provided in the present invention
Tank discharge average voltage is 3.5-4.0V；The lithium ion battery initial discharge capacity is 250-300mAh/g；The lithium ion
Battery is under 0.5C discharge-rates, and by 50 charge and discharge cycles, capacity retention ratio is more than 90%.
The present invention has the following advantages：
1, manganese is a kind of relatively cheap metal, and the present invention greatly reduces cost of material using manganese as raw material；
2, the co-precipitation and high temperature solid-state method that the present invention uses are very ripe in technique, and preparation process is simple；
3, the performance of lithium ion battery prepared with positive electrode in the present invention is remarkable, and initial discharge capacity is 250-300mAh/g,
Tertiary cathode material for example more nickelic than other high-energy-density positive electrodes improves nearly 60% energy density, compares lithium cobaltate cathode material
Improve nearly 80% energy density；Under 0.5C discharge-rates, by 50 charge and discharge cycles, capacity retention ratio is more than 90%.
Description of the drawings
Fig. 1 is spherical shape (Ni in the present invention0.166Co0.166Mn0.668)(OH)2The SEM pictures of presoma.
Fig. 2 is the SEM pictures of positive electrode in the present invention.
Fig. 3 is the XRD diffraction spectras of positive electrode in the present invention.
Fig. 4 is the lithium ion battery first charge-discharge voltage curve prepared with positive electrode in the present invention.
Fig. 5 is the capacity (mAh/g) of the lithium ion battery prepared with positive electrode in the present invention with cycle-index variation diagram.
Specific implementation mode
The present invention will be described in detail with reference to the accompanying drawings and examples.
1. the preparation of anode material of lithium battery
The method for preparing the anode material for lithium-ion batteries is as follows：
Embodiment 1
S01 prepares spherical shape (Ni0.166Co0.166Mn0.668)(OH)2Presoma
By NiSO4、CoSO4、MnSO4By cation mole concentration ratio Ni2+:Co2+:Mn2+=0.166:0.166:0.688 is made into water
Solution sets the concentration summation of all cations as 2.0mol/L；By the above-mentioned solution of 2.0L nitrogen atmosphere stirred reactor
In, control mixing speed is 1000r/min, and control heating temperature is 600 DEG C；By the NaOH solution of a concentration of 2.0mol/L of 4.2L
It instills in stirred reactor, entire instillation process needs 20h, has (Ni in reaction process0.166Co0.166Mn0.668)(OH)2Particle
Precipitation generate；While instilling NaOH solution, it is slowly dropped into the ammonium hydroxide of a concentration of 4.0mol/L, ammonium hydroxide is used for chelating
Agent is not consumptive raw material, and it is slower and slower to instill speed control；Control the instillation speed of NaOH solution and ammonium hydroxide so that
In entire reaction process, the pH value of reaction solution is 11.0, NH in stirred reactor4 +A concentration of 0.36mol/ in reaction solution
L；After reaction, precipitation is filtered, and in 110 DEG C of dryings, obtains the granular product that total amount is 4.0mol, as
(Ni0.166Co0.166Mn0.668)(OH)2Presoma；
S02 prepares layered crystal structure Li [Li0.20Ni0.133Co0.133Mn0.534]O1.995F0.005Positive electrode
By (Ni0.166Co0.166Mn0.668)(OH)2Presoma and LiOHH2O powder uniformly mixes, and mixing molar ratio is forerunner
Metal ion summation in body:Li+=0.8:1.3, mixed-powder is placed in the sintering furnace of air atmosphere and is heated, heating temperature 450
DEG C, heating time 5h；Then it is mixed with lithium fluoride, gained mixture is sintered in the sintering furnace of air atmosphere, be sintered
850 DEG C of temperature, sintering time 12h；The Li with layered crystal structure is obtained after the completion of sintering
[Li0.20Ni0.133Co0.133Mn0.534]O1.995F0.005Positive electrode, the particle shape of the positive electrode with
(Ni0.166Co0.166Mn0.668)(OH)2The particle shape of presoma is similar.
Embodiment 2
Compared with Example 1, embodiment 2 the difference is that：Heating condition, sintering condition are different in S02.The present embodiment
In, 480 DEG C of heating temperature, heating time 5h；900 DEG C of sintering temperature, sintering time 15h；It is obtained with layer after the completion of sintering
Li [the Li of shape crystal structure0.20Ni0.133Co0.133Mn0.534]O1.99F0.01Positive electrode, the particle shape of the positive electrode with
(Ni0.166Co0.166Mn0.668)(OH)2The particle shape of presoma is similar.
Fig. 2 is the SEM pictures of positive electrode in the present embodiment, it can be seen that the positive electrode granular size point prepared
Cloth is uniform, and average diameter is 5 μm.
Fig. 3 is the XRD diffraction spectras of positive electrode in the present embodiment, it can be seen that the positive electrode prepared is α-
NaFeO2Layered crystal structure.
Fig. 4 is the lithium ion battery first charge-discharge voltage curve prepared with positive electrode in the present embodiment, thus may be used
To find out the lithium-ion electric tank discharge average voltage prepared with positive electrode in the present embodiment for 3.5V.
Fig. 5 is that the capacity (mAh/g) of the lithium ion battery prepared with positive electrode in the present embodiment changes with cycle-index
Figure under 0.5C discharge-rates, by 50 charge and discharge cycles, holds it can be seen that initial discharge capacity is 275mAh/g
It measures conservation rate and is more than 90%.
Embodiment 3
Compared with Example 1, embodiment 3 the difference is that：Heating condition, sintering condition are different in S02.The present embodiment
In, 500 DEG C of heating temperature, heating time 5h；950 DEG C of sintering temperature, sintering time 18h；It is obtained with layer after the completion of sintering
Li [the Li of shape crystal structure0.20Ni0.133Co0.133Mn0.534]O1.98F0.02Positive electrode, the particle shape of the positive electrode with
(Ni0.166Co0.166Mn0.668)(OH)2The particle shape of presoma is similar.
Embodiment 4
Compared with Example 1, embodiment 4 the difference is that：Heating condition, sintering condition are different in S02.The present embodiment
In, 400 DEG C of heating temperature, heating time 5h；750 DEG C of sintering temperature, sintering time 10h；It is obtained with layer after the completion of sintering
Li [the Li of shape crystal structure0.20Ni0.133Co0.133Mn0.534]O1.995F0.005Positive electrode, the particle shape of the positive electrode with
(Ni0.166Co0.166Mn0.668)(OH)2The particle shape of presoma is similar.
Embodiment 5
Compared with Example 1, embodiment 5 the difference is that：Heating condition, sintering condition are different in S02.The present embodiment
In, 400 DEG C of heating temperature, heating time 5h；1000 DEG C of sintering temperature, sintering time 10h；It is obtained with layer after the completion of sintering
Li [the Li of shape crystal structure0.20Ni0.133Co0.133Mn0.534]O1.99F0.01Positive electrode, the particle shape of the positive electrode with
(Ni0.166Co0.166Mn0.668)(OH)2The particle shape of presoma is similar.
Embodiment 6
Compared with Example 1, embodiment 6 the difference is that：Heating condition, sintering condition are different in S02.The present embodiment
In, 400 DEG C of heating temperature, heating time 5h；750 DEG C of sintering temperature, sintering time 20h；It is obtained with layer after the completion of sintering
Li [the Li of shape crystal structure0.20Ni0.133Co0.133Mn0.534]O1.98F0.02Positive electrode, the particle shape of the positive electrode with
(Ni0.166Co0.166Mn0.668)(OH)2The particle shape of presoma is similar.
Embodiment 7
Compared with Example 1, embodiment 7 the difference is that：Heating condition, sintering condition are different in S02.The present embodiment
In, 400 DEG C of heating temperature, heating time 5h；1000 DEG C of sintering temperature, sintering time 20h；It is obtained with layer after the completion of sintering
Li [the Li of shape crystal structure0.20Ni0.133Co0.133Mn0.534]O1.992F0.008Positive electrode, the particle shape of the positive electrode with
(Ni0.166Co0.166Mn0.668)(OH)2The particle shape of presoma is similar.
Embodiment 8
Compared with Example 1, embodiment 8 the difference is that：Heating condition, sintering condition are different in S02.The present embodiment
In, 500 DEG C of heating temperature, heating time 5h；750 DEG C of sintering temperature, sintering time 10h；It is obtained with layer after the completion of sintering
Li [the Li of shape crystal structure0.20Ni0.133Co0.133Mn0.534]O1.995F0.005Positive electrode, the particle shape of the positive electrode with
(Ni0.166Co0.166Mn0.668)(OH)2The particle shape of presoma is similar.
Embodiment 9
Compared with Example 1, embodiment 9 the difference is that：Heating condition, sintering condition are different in S02.The present embodiment
In, 500 DEG C of heating temperature, heating time 5h；750 DEG C of sintering temperature, sintering time 20h；It is obtained with layer after the completion of sintering
Li [the Li of shape crystal structure0.20Ni0.133Co0.133Mn0.534]O1.99F0.01Positive electrode, the particle shape of the positive electrode with
(Ni0.166Co0.166Mn0.668)(OH)2The particle shape of presoma is similar.
Embodiment 10
Compared with Example 1, embodiment 10 the difference is that：Heating condition, sintering condition are different in S02.The present embodiment
In, 500 DEG C of heating temperature, heating time 5h；1000 DEG C of sintering temperature, sintering time 20h；It is obtained with layer after the completion of sintering
Li [the Li of shape crystal structure0.20Ni0.133Co0.133Mn0.534]O1.98F0.02Positive electrode, the particle shape of the positive electrode with
(Ni0.166Co0.166Mn0.668)(OH)2The particle shape of presoma is similar.
The chemical formula of positive electrode obtained by the corresponding experiment condition of embodiment and preparation：
2. the preparation of lithium ion battery
Preparation method of lithium ion battery：By positive electrode, conductive black, PVDF binders according to mass ratio 85:8:7 ratio with
A certain amount of NMP carries out homogenate coating together, and it is 20mg/cm to be prepared into surface density2Positive plate, roll-in is carried out after dry and is cut out
At the disk of diameter 16mm, lithium piece is assembled into 2032 button cells as cathode.
Comparative example 1 is conventional lithium nickelate positive electrode, and comparative example 2 is conventional lithium cobaltate cathode material, comparative example 3,
Comparative example 4 is respectively that application number 201610284398.5 is entitled《A kind of synthetic method of high-performance lithium-rich manganese-based anode material》Specially
2wt.%Al in profit2O3-Li1.2Ni0.15Co0.10Mn0.55O2、1wt.%Al2O3-Li1.2Ni0.15Co0.10Mn0.55O2Nano aluminium oxide
Positive electrode after cladding.
By the positive electrode in anode material for lithium-ion batteries obtained, comparative example in embodiment according to above-mentioned lithium-ion electric
Lithium ion battery is respectively prepared in the preparation method in pond.
3. test
The lithium ion battery being prepared is used into Biologic（VMP-3）Battery test system carry out constant-current charge electric discharge and
Loop test, test voltage are（2.5-4.8 V）, test result is as follows under 0.5C discharge-rates table.
By test result it is found that the lithium ion battery in embodiment has excellent electrochemistry cycle performance, initial discharge
Capacity is all higher than 250mAh/g, and under 0.5C discharge-rates, by 50 charge and discharge cycles, capacity retention ratio is all higher than 90%.
In comparative example, conventional lithium nickelate and the lithium ion battery that cobalt acid lithium is positive electrode preparation, battery initial discharge hold
Amount is below 200 mAh/g, and after 50 charge and discharge cycles, capacity retention ratio is below 90%；With 2wt.%Al2O3-
Li1.2Ni0.15Co0.10Mn0.55O2、1wt.%Al2O3-Li1.2Ni0.15Co0.10Mn0.55O2Positive electrode after nano aluminium oxide cladding
Although the lithium ion battery of preparation, by 50 charge and discharge cycles, capacity retention ratio is all higher than 90%, and battery initial discharge holds
Amount is far below embodiment.
By taking embodiment 2 as an example, which is parametric results best in embodiment, and initial discharge capacity is 275 mAh/
G is more than the lithium ion battery in comparative example.Under 0.5C discharge-rates, embodiment 2 passes through 50 charge and discharge cycles, and capacity is protected
Holdup is 94.5%.There are in table data can be seen that the capacity of lithium ion battery and cycle performance in the embodiment of the present invention all apparent
Better than comparative example.
Finally, it should be noted that above example be only to illustrate the embodiment of the present invention technical solution rather than to its into
Row limitation, although the embodiment of the present invention is described in detail with reference to preferred embodiment, those skilled in the art
It should be understood that the technical solution of the embodiment of the present invention can be still modified or replaced equivalently, and these are changed or wait
The range of modified technical solution disengaging technical solution of the embodiment of the present invention cannot also be made with replacement.
Claims (10)
1. a kind of anode material for lithium-ion batteries, chemical formula is Li [Li0.20Ni0.8xCo0.8yMn0.8z]O2-aFa, wherein 0.1≤x
≤ 0.2,0.1≤y≤0.2, x+y+z=1,0.002≤a≤0.02.
2. anode material for lithium-ion batteries as described in claim 1, it is characterised in that：The positive electrode is layered crystal knot
Structure.
3. anode material for lithium-ion batteries as described in claim 1, it is characterised in that：The positive electrode average diameter of particles is
4-6μm；The positive electrode particle compacted density is 1.40-1.60g/cm3。
4. a kind of preparation method of anode material for lithium-ion batteries, it is characterised in that：It is first prepared using co-electrodeposition method spherical
(NixCoyMnz)(OH)2Presoma, then the lithium-rich manganese-based anode material for adulterating fluorine element is prepared using high temperature solid-state method, change
Formula is Li [Li0.20Ni0.8xCo0.8yMn0.8z]O2-aFa。
5. the preparation method of anode material for lithium-ion batteries as claimed in claim 4, which is characterized in that include the following steps：
S01, spherical (NixCoyMnz)(OH)2The preparation of presoma：
Nickel sulfate, cobaltous sulfate, manganese sulfate are pressed into cation mole concentration ratio Ni2+:Co2+:Mn2+=x:y:Z is made into aqueous solution, wherein
0.1≤x≤0.2,0.1≤y≤0.2, x+y+z=1 set the concentration summation of all cations as 2.0mol/L；
By above-mentioned solution agitating and heating in an inert atmosphere, while sodium hydroxide solution and ammonium hydroxide are instilled, pH value of reaction system model
It encloses for 10-11.5, spherical (Ni is made in filtration drying after the reaction was completexCoyMnz)(OH)2Granular precursor, wherein 0.1≤x≤
0.2,0.1≤y≤0.2, x+y+z=1；
S02, layered crystal structure Li [Li0.20Ni0.8xCo0.8yMn0.8z]O2-aFaThe preparation of positive electrode：
Granular precursor made from S01 is mixed with lithium hydroxide, metal ion summation and lithium ion rubs wherein in presoma
You are than being (0.6-0.8): (1.0-1.5)；
Said mixture is heated into 5h for 400-500 DEG C in atmosphere furnace, lithium fluoride is then mixed into and continues to be sintered at 750-1000 DEG C
Layered crystal structure Li [Li are made in 10-20h0.20Ni0.8xCo0.8yMn0.8z]O2-aFaPositive electrode particle, wherein 0.1≤x≤
0.2,0.1≤y≤0.2, x+y+z=1.
6. the preparation method of anode material for lithium-ion batteries as claimed in claim 5, it is characterised in that：Indifferent gas described in S01
Atmosphere is nitrogen atmosphere；Mixing speed described in S01 is 900-1100r/min；Heating temperature described in S01 is 500-600 DEG C；
Atmosphere is air atmosphere in atmosphere furnace described in S02.
7. the preparation method of anode material for lithium-ion batteries as claimed in claim 5, it is characterised in that：Hydroxide described in S01
A concentration of 2.0mol/L of sodium solution；Ammonium hydroxide molar concentration described in S01 is 4.0mol/L；During ammonium hydroxide described in S01 instills
Control NH4 +A concentration of 0.30-0.36mol/L in reaction solution.
8. the preparation method of anode material for lithium-ion batteries as claimed in claim 5, it is characterised in that：It is obtained in the S01
(NixCoyMnz)(OH)2Granular precursor diameter range is 4-6 μm.
9. a kind of lithium ion battery, it is characterised in that：The positive electrode of the lithium ion battery is any institutes of such as claim 1-3
State anode material for lithium-ion batteries.
10. lithium ion battery as claimed in claim 9, it is characterised in that：The lithium-ion electric tank discharge average voltage is 3.5-
4.0V；The lithium ion battery initial discharge capacity is 250-300mAh/g；The lithium ion battery under 0.5C discharge-rates,
By 50 charge and discharge cycles, capacity retention ratio is more than 90%.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111435735A (en) * | 2019-12-27 | 2020-07-21 | 蜂巢能源科技有限公司 | Lithium-rich manganese-based positive electrode material and preparation method and application thereof |
| CN112701273A (en) * | 2020-12-29 | 2021-04-23 | 国联汽车动力电池研究院有限责任公司 | Preparation method of fluorine-doped lithium-rich manganese-based positive electrode material |
| CN114864908A (en) * | 2022-05-31 | 2022-08-05 | 蜂巢能源科技股份有限公司 | Lithium-rich cathode material and preparation method and application thereof |
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2018
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111435735A (en) * | 2019-12-27 | 2020-07-21 | 蜂巢能源科技有限公司 | Lithium-rich manganese-based positive electrode material and preparation method and application thereof |
| CN111435735B (en) * | 2019-12-27 | 2022-10-25 | 蜂巢能源科技有限公司 | Lithium-rich manganese-based positive electrode material and preparation method and application thereof |
| CN112701273A (en) * | 2020-12-29 | 2021-04-23 | 国联汽车动力电池研究院有限责任公司 | Preparation method of fluorine-doped lithium-rich manganese-based positive electrode material |
| CN114864908A (en) * | 2022-05-31 | 2022-08-05 | 蜂巢能源科技股份有限公司 | Lithium-rich cathode material and preparation method and application thereof |
| CN114864908B (en) * | 2022-05-31 | 2024-04-05 | 蜂巢能源科技股份有限公司 | Lithium-rich positive electrode material and preparation method and application thereof |
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