CN108736002A - A kind of part carbon coating type richness lithium solid solution oxysulfide positive electrode and preparation method thereof - Google Patents
A kind of part carbon coating type richness lithium solid solution oxysulfide positive electrode and preparation method thereof Download PDFInfo
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- CN108736002A CN108736002A CN201810543224.5A CN201810543224A CN108736002A CN 108736002 A CN108736002 A CN 108736002A CN 201810543224 A CN201810543224 A CN 201810543224A CN 108736002 A CN108736002 A CN 108736002A
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- Prior art keywords
- oxysulfide
- solid solution
- positive electrode
- mns
- carbon coating
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 57
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 52
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 239000006104 solid solution Substances 0.000 title claims abstract description 39
- 239000011248 coating agent Substances 0.000 title claims abstract description 35
- 238000000576 coating method Methods 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 239000000463 material Substances 0.000 claims abstract description 27
- 238000001238 wet grinding Methods 0.000 claims abstract description 5
- 238000001035 drying Methods 0.000 claims abstract description 4
- 238000003746 solid phase reaction Methods 0.000 claims abstract description 4
- FOOYZGHHJWWMKM-UHFFFAOYSA-N [S-2].[Mn+2].[Li+] Chemical compound [S-2].[Mn+2].[Li+] FOOYZGHHJWWMKM-UHFFFAOYSA-N 0.000 claims abstract description 3
- 238000009837 dry grinding Methods 0.000 claims abstract description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- 239000011572 manganese Substances 0.000 claims description 16
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- 229910052786 argon Inorganic materials 0.000 claims description 7
- 239000007789 gas Substances 0.000 claims description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 239000002002 slurry Substances 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 4
- 229920002472 Starch Polymers 0.000 claims description 4
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 4
- 229930006000 Sucrose Natural products 0.000 claims description 4
- 239000006230 acetylene black Substances 0.000 claims description 4
- 239000008103 glucose Substances 0.000 claims description 4
- 239000008107 starch Substances 0.000 claims description 4
- 235000019698 starch Nutrition 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 239000005720 sucrose Substances 0.000 claims description 4
- -1 SuperP Chemical compound 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 229910002804 graphite Inorganic materials 0.000 claims description 3
- 239000010439 graphite Substances 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 2
- 229910052797 bismuth Inorganic materials 0.000 claims description 2
- 229910052792 caesium Inorganic materials 0.000 claims description 2
- 235000019441 ethanol Nutrition 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 239000005416 organic matter Substances 0.000 claims description 2
- 239000005011 phenolic resin Substances 0.000 claims description 2
- 229920001568 phenolic resin Polymers 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 229910052701 rubidium Inorganic materials 0.000 claims description 2
- 229910052707 ruthenium Inorganic materials 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 229910052723 transition metal Inorganic materials 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- 239000012071 phase Substances 0.000 claims 1
- 239000011149 active material Substances 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 description 20
- 230000000052 comparative effect Effects 0.000 description 18
- 238000002791 soaking Methods 0.000 description 16
- 238000002156 mixing Methods 0.000 description 13
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 12
- 239000001301 oxygen Substances 0.000 description 12
- 229910052760 oxygen Inorganic materials 0.000 description 12
- 239000000843 powder Substances 0.000 description 11
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 9
- 239000000919 ceramic Substances 0.000 description 8
- 238000006073 displacement reaction Methods 0.000 description 8
- 238000000227 grinding Methods 0.000 description 8
- 229910001416 lithium ion Inorganic materials 0.000 description 7
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- QDZOEBFLNHCSSF-PFFBOGFISA-N (2S)-2-[[(2R)-2-[[(2S)-1-[(2S)-6-amino-2-[[(2S)-1-[(2R)-2-amino-5-carbamimidamidopentanoyl]pyrrolidine-2-carbonyl]amino]hexanoyl]pyrrolidine-2-carbonyl]amino]-3-(1H-indol-3-yl)propanoyl]amino]-N-[(2R)-1-[[(2S)-1-[[(2R)-1-[[(2S)-1-[[(2S)-1-amino-4-methyl-1-oxopentan-2-yl]amino]-4-methyl-1-oxopentan-2-yl]amino]-3-(1H-indol-3-yl)-1-oxopropan-2-yl]amino]-1-oxo-3-phenylpropan-2-yl]amino]-3-(1H-indol-3-yl)-1-oxopropan-2-yl]pentanediamide Chemical compound C([C@@H](C(=O)N[C@H](CC=1C2=CC=CC=C2NC=1)C(=O)N[C@@H](CC(C)C)C(=O)N[C@@H](CC(C)C)C(N)=O)NC(=O)[C@@H](CC=1C2=CC=CC=C2NC=1)NC(=O)[C@H](CCC(N)=O)NC(=O)[C@@H](CC=1C2=CC=CC=C2NC=1)NC(=O)[C@H]1N(CCC1)C(=O)[C@H](CCCCN)NC(=O)[C@H]1N(CCC1)C(=O)[C@H](N)CCCNC(N)=N)C1=CC=CC=C1 QDZOEBFLNHCSSF-PFFBOGFISA-N 0.000 description 4
- 229910001216 Li2S Inorganic materials 0.000 description 4
- 102100024304 Protachykinin-1 Human genes 0.000 description 4
- 101800003906 Substance P Proteins 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 229910052808 lithium carbonate Inorganic materials 0.000 description 4
- CADICXFYUNYKGD-UHFFFAOYSA-N sulfanylidenemanganese Chemical compound [Mn]=S CADICXFYUNYKGD-UHFFFAOYSA-N 0.000 description 4
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000000498 ball milling Methods 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 3
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 2
- GLNWILHOFOBOFD-UHFFFAOYSA-N lithium sulfide Chemical compound [Li+].[Li+].[S-2] GLNWILHOFOBOFD-UHFFFAOYSA-N 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 229940093474 manganese carbonate Drugs 0.000 description 2
- 239000011656 manganese carbonate Substances 0.000 description 2
- 235000006748 manganese carbonate Nutrition 0.000 description 2
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 description 2
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 2
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- FGDZQCVHDSGLHJ-UHFFFAOYSA-M rubidium chloride Chemical compound [Cl-].[Rb+] FGDZQCVHDSGLHJ-UHFFFAOYSA-M 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 1
- MULYSYXKGICWJF-UHFFFAOYSA-L cobalt(2+);oxalate Chemical compound [Co+2].[O-]C(=O)C([O-])=O MULYSYXKGICWJF-UHFFFAOYSA-L 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical class [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910002102 lithium manganese oxide Inorganic materials 0.000 description 1
- VLXXBCXTUVRROQ-UHFFFAOYSA-N lithium;oxido-oxo-(oxomanganiooxy)manganese Chemical compound [Li+].[O-][Mn](=O)O[Mn]=O VLXXBCXTUVRROQ-UHFFFAOYSA-N 0.000 description 1
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 1
- HOOANQZZUGPTRH-UHFFFAOYSA-N molybdenum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Mo+3].[Mo+3] HOOANQZZUGPTRH-UHFFFAOYSA-N 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 229940102127 rubidium chloride Drugs 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 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
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- 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
- H01M4/485—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
- 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
-
- 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
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/581—Chalcogenides or intercalation compounds thereof
- H01M4/5815—Sulfides
-
- 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
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
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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
- H01M6/00—Primary cells; Manufacture thereof
- H01M6/14—Cells with non-aqueous electrolyte
- H01M6/16—Cells with non-aqueous electrolyte with organic electrolyte
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- 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
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Composite Materials (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention discloses a kind of local carbon coating type richness lithium solid solution oxysulfide positive electrodes and preparation method thereof, by Li2+αMnS3Carbon source is added in lithium sulfide manganese material, by dry grinding, obtains carbon-coated Li2+αMnS3Presoma, or by wet grinding, drying, obtain carbon-coated Li2+αMnS3Presoma；By above-mentioned presoma and Li1+βTm(1‑γ)MγO2It is uniformly mixed according to design proportion, carries out low-temperature solid phase reaction under an inert atmosphere to get to cladded type richness lithium solid solution oxysulfide positive electrode.The positive pole active material for lithium cell such as lithium primary battery, lithium secondary battery, lithium rechargeable battery are can be used as, there is the excellent charge-discharge performances such as specific capacity is high, electric conductivity is high, has extended cycle life.
Description
Technical field
The present invention relates to a kind of lithium ion battery material, especially a kind of local carbon coating type richness lithium solid solution oxysulfide
Positive electrode and preparation method thereof.
Background technology
With the continuous promotion and popularization of new energy vehicle, the demand for promoting course continuation mileage is more and more urgent, and it is new to become development
One of the demand of energy automobile most critical.Power battery is the core of new-energy automobile, wherein lithium ion battery cost,
There is apparent advantage, the convenience that will significantly promote new-energy automobile economy and use, lithium in terms of energy density
Positive electrode is deciding factor in ion battery systems.To increase course continuation mileage, it is necessary to increase carrying electrokinetic cell system and deposit
The energy of storage, under the premise of not dramatically increasing newly energy vehicle weight and volume, it is necessary to improve the ratio energy and energy of power battery
Metric density.If pure electric automobile course continuation mileage reaches 400 kilometers, electrokinetic cell system than energy demand be promoted to 250Wh/kg with
On, single battery need to promote 350Wh/kg than energy.
Invention content
The technical problem to be solved by the present invention is to, for obtain high-energy-density density anode material for lithium-ion batteries,
The rich lithium solid solution oxysulfide positive electrode and its preparation side that a kind of specific capacity is high, electric conductivity is high, cycle performance is excellent are provided
Method.
In order to solve the above-mentioned technical problem, the technical solution adopted by the present invention is：A kind of part carbon coating type richness lithium solid solution
Body oxysulfide positive electrode, stoichiometric equation aLi2+αMnS3Cλ·(1-a)Li1+βTm(1-γ)MγO2Or general formula Li1+x(1-
a)[MnaTm(1-γ)MγO2]S3aCλ；
Wherein：0 < a < 1, -0.2≤α≤0.2, -0.1≤β≤0.1,0≤γ≤0.1,0 12 λ of </M (Li2+αMnS3)
≤ 0.2, x=a (1+ alpha-betas)+β；
M(Li2+αMnS3) it is Li2+αMnS3Molecular weight；
TmFor one or more combinations in transition metal element Ni, Co, Mn；
M is one or more combinations in Na, K, Rb, Cs, Sc, Nb, Bi, Fe, Mo, Ti, Al, Mg, Zn, V, Zr, Ru.
The preparation method of above-mentioned part carbon coating type richness lithium solid solution oxysulfide positive electrode, includes the following steps：
1) by Li2+αMnS3Carbon source is added in lithium sulfide manganese material, by dry grinding, obtains carbon-coated Li2+αMnS3Before
Body is driven, or by wet grinding, drying, obtains carbon-coated Li2+αMnS3Presoma；
2) by above-mentioned presoma and Li1+βTm(1-γ)MγO2It uniformly mixes, carries out under an inert atmosphere low according to design proportion
Warm solid phase reaction is to get to cladded type richness lithium solid solution oxysulfide positive electrode.
Carbon source described in step 1) is simple substance carbon and/or the organic matter of carbon elements.
Carbon source described in step 1) is one in acetylene black, SuperP, graphite, glucose, sucrose, starch, phenolic resin
Kind or several combinations.
Wet grinding medium described in step 1) is one kind in deionized water, ethyl alcohol, methanol, nmp solvent, and slurry contains admittedly
Amount is 20%~80%.
Low-temperature solid phase reaction described in step 2), reaction temperature are 200 DEG C~400 DEG C, and the reaction time is 2h~for 24 hours.
Inert atmosphere described in step 2) is nitrogen or argon gas.
The beneficial effects of the invention are as follows：Preparation process is simple, and raw material resources are abundant, and of low cost, product can be used as lithium one
The positive electrode active materials of primary cell, lithium secondary battery, lithium ion battery secondary cell are applied to lithium battery or lithium ion secondary electricity
Chi Zhong has higher charge/discharge capacity, cycle performance and high rate performance, is applied to new energy vehicle field, is expected to realize body electricity
Pond need to reach 350Wh/kg or more than energy.It can also be applied to various uses chemical energy storage field of power supplies simultaneously, as electronics is set
The extensive energy storage device such as standby, electric tool and solar power generation, wind-power electricity generation.
Description of the drawings
Fig. 1 is a kind of situation stream of local carbon coating type richness lithium solid solution oxysulfide positive electrode preparation process of the present invention
Cheng Tu.
Fig. 2 is the local carbon coating type richness lithium solid solution oxysulfide positive electrode preparation process another kind situation of the present invention
Flow chart.
Specific implementation mode
As shown in Figure 1, 2, with reference to specific embodiment to local carbon coating type richness lithium solid solution oxysulfide of the invention
Positive electrode preparation is described in further detail：
Comparative example 1
A kind of preparation method of part carbon coating type richness lithium solid solution oxysulfide positive electrode, includes the following steps：
1) according to 1:1:A 0.1 mole metering ratio weighs manganese sulfide MnS2, lithium sulfide Li2S, lithium carbonate Li2CO3Powder adds
Enter high speed mixer, high speed dispersion 30min, the powder material being uniformly mixed.
2) material after above-mentioned mixing is packed into ceramic saggar, be placed in box atmosphere furnace, is passed through in nitrogen displacement burner hearth
Air is to oxygen content 1% hereinafter, opening heating system.Heating temperature is 950 DEG C, soaking time 12h, and pyroreaction is completed
Postcooling, grinding, obtains material P1.
3) it is Li according to atomic ratio by lithium carbonate, cobalt oxalate, manganese nitrate, nickel hydroxide, butyl titanate:(Co+Ni+Mn+
Ti)=1.1:1, Co:Ni:Mn:Ti=2:5:2.9:0.01, corresponding raw material is weighed, high speed mixer is added, is uniformly mixed；
4) above-mentioned powder material is packed into ceramic saggar, is placed in box atmosphere furnace, is roasted in air atmosphere, roasts
1000 DEG C, soaking time 6h of temperature, pyroreaction complete postcooling, and grinding obtains material P2.
5) according to molar ratio 1:9 weigh the P1 and P2 of corrresponding quality, after being sufficiently mixed, are placed in box atmosphere furnace, are passed through
Argon gas replace burner hearth in air to oxygen content 1% hereinafter, open heating system.Heating temperature is 200 DEG C, and soaking time is
For 24 hours, pyroreaction completes postcooling, obtains rich lithium solid solution oxysulfide positive electrode 0.1Li2.2MnS3·
0.9Li1.1Co0.2Ni0.5Mn2.9Ti0.01O2。
Embodiment 1
A kind of preparation method of part cladded type richness lithium solid solution oxysulfide positive electrode, includes the following steps：
1) P1 and acetylene black are weighed after using the method in comparative example 1 to obtain Substance P 1, the mass ratio of acetylene black and P1 are
5:95, ball milling mixing obtains carbon coating Li2.2MnS3C0.77Presoma；
2) according to molar ratio 1:9 weigh the carbon coating Li of corrresponding quality2.2MnS3C0.77Presoma and the P2 in comparative example, fill
It after dividing mixing, is placed in box atmosphere furnace, the air being passed through in argon gas displacement burner hearth is heated 1% hereinafter, opening to oxygen content
System.Heating temperature is 200 DEG C, and soaking time is that for 24 hours, pyroreaction completes postcooling, and it is solid to obtain local carbon coating type richness lithium
Solution oxysulfide positive electrode 0.1Li2.2MnS3C0.77·0.9Li1.1Co0.2Ni0.5Mn2.9Ti0.01O2。
Comparative example 2
A kind of preparation method of richness lithium solid solution oxysulfide positive electrode, includes the following steps：
1) according to MnS2：Li2S=1:1 mole metering is than weighing manganese sulfide and vulcanizing lithium powder, addition high speed mixer,
High speed dispersion 30min, the powder material being uniformly mixed.
2) material after above-mentioned mixing is packed into ceramic saggar, be placed in tube-type atmosphere furnace, is passed through in nitrogen displacement burner hearth
Air is to oxygen content 1% hereinafter, opening heating system.Heating temperature is 500 DEG C, and soaking time is that for 24 hours, pyroreaction is completed
Postcooling, grinding, obtains material P1.
3) it is Li according to atomic ratio by lithium hydroxide, manganese carbonate, nickel chloride, alundum (Al2O3), sodium hydroxide:(Ni+Mn+
Al+Na)=1:1, Ni:Mn:Al:Na=1.5:0.4:0.05:0.05, corresponding raw material is weighed, high speed mixer, mixing is added
Uniformly；
4) above-mentioned powder material is packed into ceramic saggar, is placed in tube-type atmosphere furnace, is roasted in air atmosphere, roasts
500 DEG C of temperature, soaking time are that for 24 hours, pyroreaction completes postcooling, and grinding obtains material P2.
5) according to molar ratio 1:1 weighs the P1 and P2 of corrresponding quality, after being sufficiently mixed, is placed in tube-type atmosphere furnace, is passed through
Nitrogen replace burner hearth in air to oxygen content 1% hereinafter, open heating system.Heating temperature is 500 DEG C, and soaking time is
2h, pyroreaction complete postcooling, obtain rich lithium solid solution oxysulfide positive electrode 0.5Li2MnS3·
0.5LiNi1.5Mn0.4Al0.05Na0.05O2。
Embodiment 2
A kind of preparation method of part carbon coating type richness lithium solid solution oxysulfide positive electrode, includes the following steps：
1) P1 and glucose are weighed after using the method in comparative example 2 to obtain Substance P 1, the carbon containing quality of glucose and P1's
Mass ratio is 10:90, the deionized water of certain mass is added so that slurry solid content is 20%, ground and mixed, and 105 DEG C are fully
It is dry, obtain carbon coating Li1.9MnS3C1.52Presoma；
2) according to molar ratio 1:1 weighs the carbon coating Li of corrresponding quality1.9MnS3C1.52Presoma and the P2 in comparative example, fill
It after dividing mixing, is placed in box atmosphere furnace, the air being passed through in argon gas displacement burner hearth is heated 1% hereinafter, opening to oxygen content
System.Heating temperature is 400 DEG C, soaking time 2h, and pyroreaction completes postcooling, obtains local carbon coating type richness lithium solid solution
Body oxysulfide positive electrode 0.5Li2MnS3C1.52·0.5LiNi1.5Mn0.4Al0.05Na0.05O2。
Comparative example 3
A kind of preparation method of richness lithium solid solution oxysulfide positive electrode, includes the following steps：
1) according to MnS2：Li2S：S=0.9:1:A 0.1 mole metering ratio weighs manganese sulfide, lithium sulfide and simple substance sulfur powder,
High speed mixer, high speed dispersion 30min, the powder material being uniformly mixed is added.
2) material after above-mentioned mixing is packed into ceramic saggar, be placed in bell-type atmosphere furnace, is passed through in nitrogen displacement burner hearth
Air is to oxygen content 1% hereinafter, opening heating system.Heating temperature is 1100 DEG C, soaking time 2h, and pyroreaction is completed
Postcooling, grinding, obtains material P1.
3) it is Li according to atomic ratio by lithium nitrate, nickel hydroxide, molybdenum sesquioxide, ammonium vanadate, rubidium chloride:(Ni+Mo+V+
Ru)=0.9:1, Ni:Mo:V:Ru=0.95:0.01:0.03:0.01, corresponding raw material is weighed, high speed mixer, mixing is added
Uniformly；
4) above-mentioned powder material is packed into ceramic saggar, is placed in bell-type atmosphere furnace, is roasted in air atmosphere, roasts
1000 DEG C, soaking time 8h of temperature, pyroreaction complete postcooling, and grinding obtains material P2.
5) according to molar ratio 7:3 weigh the P1 and P2 of corrresponding quality, after being sufficiently mixed, are placed in bell-type atmosphere furnace, are passed through
Nitrogen replace burner hearth in air to oxygen content 1% hereinafter, open heating system.Heating temperature is 300 DEG C, and soaking time is
6h, pyroreaction complete postcooling, obtain rich lithium solid solution oxysulfide positive electrode 0.7Li1.8MnS3·
0.3LiNi0.95Mo0.01V0.03Ru0.01O2。
Embodiment 3
A kind of preparation method of part carbon coating type richness lithium solid solution oxysulfide positive electrode, includes the following steps：
1) after using the method in comparative example 3 to obtain Substance P 1, P1, starch and graphite, the carbon containing quality of starch and stone are weighed
The gross mass of ink and the mass ratio of P1 are 20:80, NMP is added so that slurry solid content is 40%, and after ball milling mixing, 110 DEG C are filled
Divide drying, obtains carbon coating Li2MnS3C3.43Presoma；
2) according to molar ratio 7:3 weigh the carbon coating Li of corrresponding quality2MnS3C3.43Presoma and the P2 in comparative example, fill
It after dividing mixing, is placed in box atmosphere furnace, the air being passed through in argon gas displacement burner hearth is heated 1% hereinafter, opening to oxygen content
System.Heating temperature is 400 DEG C, soaking time 2h, and pyroreaction completes postcooling, obtains local carbon coating type richness lithium solid solution
Body oxysulfide positive electrode 0.7Li1.8MnS3C3.43·0.3LiNi0.95Mo0.01V0.03Ru0.01O2。
Comparative example 4
A kind of preparation method of richness lithium solid solution oxysulfide positive electrode, includes the following steps：
1) according to MnS2：Li2S=1:1 mole metering is than weighing manganese sulfide and vulcanizing lithium powder, addition high speed mixer,
High speed dispersion 30min, the powder material being uniformly mixed.
2) material after above-mentioned mixing is packed into ceramic saggar, be placed in bell-type atmosphere furnace, is passed through in nitrogen displacement burner hearth
Air is to oxygen content 1% hereinafter, opening heating system.Heating temperature is 800 DEG C, soaking time 4h, and pyroreaction is completed
Postcooling, grinding, obtains material P1.
3) it is Li according to atomic ratio by lithium carbonate, four cobalt oxides, manganese carbonate, nickel chloride:(Co+Ni+Mn)=1.05:1,
Co:Ni:Mn=1:8:1, corresponding raw material is weighed, high speed mixer is added, is uniformly mixed；
4) above-mentioned powder material is packed into ceramic saggar, is placed in bell-type atmosphere furnace, is roasted in air atmosphere, roasts
1000 DEG C, soaking time 8h of temperature, pyroreaction complete postcooling, and grinding obtains material P2.
5) according to molar ratio 2:8 weigh the P1 and P2 of corrresponding quality, after being sufficiently mixed, are placed in bell-type atmosphere furnace, are passed through
Nitrogen replace burner hearth in air to oxygen content 1% hereinafter, open heating system.Heating temperature is 350 DEG C, and soaking time is
4h, pyroreaction complete postcooling, obtain type richness lithium solid solution oxysulfide positive electrode 0.2Li2MnS3·
0.8LiCo0.1Ni0.8Mn0.1O2。
Embodiment 4
A kind of preparation method of part carbon coating type richness lithium solid solution oxysulfide positive electrode, includes the following steps：
1) after using the method in comparative example 4 to obtain Substance P 1, P1, sucrose, the quality of sucrose carbon containing quality and P1 are weighed
Than being 8:92, absolute ethyl alcohol is added so that slurry solid content is 80%, and after ball milling mixing, 80 DEG C are fully dry, obtain carbon coating
Li2MnS3C1.19Presoma；
2) according to molar ratio 7:3 weigh the carbon coating Li of corrresponding quality2MnS3C3.43Presoma and the P2 in comparative example, fill
It after dividing mixing, is placed in box atmosphere furnace, the air being passed through in argon gas displacement burner hearth is heated 1% hereinafter, opening to oxygen content
System.Heating temperature is 350 DEG C, soaking time 4h, and pyroreaction completes postcooling, is obtaining rich lithium solid solution oxysulfide just
Pole material 0.2Li2MnS3C1.19·0.8LiCo0.1Ni0.8Mn0.1O2。
Experimental conditions：Local carbon coating type
It is just that table 1, which is listed using local carbon coating type richness lithium solid solution oxysulfide material made from above-described embodiment,
Pole, metal lithium sheet be cathode prepare button cell, under 0.1C current ratios the reversible specific capacity of (1C=420mAh/g) and
Coulombic efficiency for the first time.The test condition of button cell is LR2032,0.1CC/0.1DC 2.0V~4.8V, vs.Li+/Li.It uses
Charging/discharging apparatus be blue electric charge and discharge instrument.
1 charge-discharge property contrast table of table
| Sample number into spectrum | 0.1C reversible specific capacities (mAh/g) | Coulombic efficiency (%) for the first time |
| Embodiment 1 | 270 | 88.10 |
| Comparative example 1 | 263 | 87.70 |
| Embodiment 2 | 335 | 90.20 |
| Comparative example 2 | 227 | 89.40 |
| Embodiment 3 | 365 | 91.50 |
| Comparative example 3 | 359 | 90.05 |
| Embodiment 4 | 304 | 89.70 |
| Comparative example 4 | 274 | 87.37 |
As can be seen from the data in the table, local carbon coating type richness lithium solid solution oxysulfide positive electrode prepared by the present invention
It is promoted with the coulombic efficiency for the first time than comparative example.May be since carbon coating layer is covered in lithium manganese oxide surface, every
The corrosion of electrolyte absolutely, reduces the generation of side reaction.
It is just that table 2, which is listed using local carbon coating type richness lithium solid solution oxysulfide material made from above-described embodiment,
Pole, metal lithium sheet are 50 weeks cycle performances of button cell prepared by cathode.The test condition of battery is, LR 2032,2.0V~
4.8V vs.Li+/Li：1CC/1DC.The charging/discharging apparatus used is blue electric charge and discharge instrument.
2 cycle performance contrast table of table
As can be seen from the data in the table, the local cladded type richness lithium solid solution oxysulfide positive electrode for preparing of the present invention compared with
Comparative example is promoted in terms of capacity retention ratio and voltage retention.This may be since carbon coating layer stabilizes lithium manganese sulphur
The S problems of dissolution that compound may occur during charge and discharge cycles is alleviated.
In conclusion present disclosure is not limited in the above embodiments, the knowledgeable people in same area can
Can propose other embodiments easily within the technological guidance's thought of the present invention, but this embodiment is included in this hair
Within the scope of bright.
Claims (7)
1. a kind of part carbon coating type richness lithium solid solution oxysulfide positive electrode, which is characterized in that its stoichiometric equation is
aLi2+αMnS3Cλ·(1-a)Li1+βTm(1-γ)MγO2Or general formula Li1+x(1-a)[MnaTm(1-γ)MγO2]S3aCλ；
Wherein：0 < a < 1, -0.2≤α≤0.2, -0.1≤β≤0.1,0≤γ≤0.1,0 12 λ of </M (Li2+αMnS3)≤0.2,
X=a (1+ alpha-betas)+β；
M(Li2+αMnS3) it is Li2+αMnS3Molecular weight；
TmFor one or more combinations in transition metal element Ni, Co, Mn；
M is one or more combinations in Na, K, Rb, Cs, Sc, Nb, Bi, Fe, Mo, Ti, Al, Mg, Zn, V, Zr, Ru.
2. the preparation method of part carbon coating type richness lithium solid solution oxysulfide positive electrode as described in claim 1, feature
It is, includes the following steps：
1) by Li2+αMnS3Carbon source is added in lithium sulfide manganese material, by dry grinding, obtains carbon-coated Li2+αMnS3Forerunner
Body, or by wet grinding, drying, obtain carbon-coated Li2+αMnS3Presoma；
2) by above-mentioned presoma and Li1+βTm(1-γ)MγO2It is uniformly mixed according to design proportion, carries out low-temperature solid under an inert atmosphere
Phase reaction is to get to cladded type richness lithium solid solution oxysulfide positive electrode.
3. the preparation method of local carbon coating type richness lithium solid solution oxysulfide positive electrode according to claim 2, special
Sign is that the carbon source described in step 1) is simple substance carbon and/or the organic matter of carbon elements.
4. the preparation method of local carbon coating type richness lithium solid solution oxysulfide positive electrode according to claim 3, special
Sign is that the carbon source described in step 1) is one kind in acetylene black, SuperP, graphite, glucose, sucrose, starch, phenolic resin
Or several combination.
5. the preparation method of local carbon coating type richness lithium solid solution oxysulfide positive electrode according to claim 2, special
Sign is that the wet grinding medium described in step 1) is one kind in deionized water, ethyl alcohol, methanol, nmp solvent, and slurry contains admittedly
Amount is 20%~80%.
6. the preparation method of local carbon coating type richness lithium solid solution oxysulfide positive electrode according to claim 2, special
Sign is, the low-temperature solid phase reaction described in step 2), and reaction temperature is 200 DEG C~400 DEG C, and the reaction time is 2h~for 24 hours.
7. the preparation method of local carbon coating type richness lithium solid solution oxysulfide positive electrode according to claim 2, special
Sign is that the inert atmosphere described in step 2) is nitrogen or argon gas.
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