CN101219806B - Anode material of lithium cell and solid-phase sintering production method at high temperature - Google Patents
Anode material of lithium cell and solid-phase sintering production method at high temperature Download PDFInfo
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- CN101219806B CN101219806B CN2008100188068A CN200810018806A CN101219806B CN 101219806 B CN101219806 B CN 101219806B CN 2008100188068 A CN2008100188068 A CN 2008100188068A CN 200810018806 A CN200810018806 A CN 200810018806A CN 101219806 B CN101219806 B CN 101219806B
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- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 40
- 238000005245 sintering Methods 0.000 title claims abstract description 39
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 239000010405 anode material Substances 0.000 title claims abstract description 25
- 239000007790 solid phase Substances 0.000 title claims description 10
- 238000004519 manufacturing process Methods 0.000 title claims description 8
- 239000000843 powder Substances 0.000 claims abstract description 31
- 239000002245 particle Substances 0.000 claims abstract description 29
- 238000001816 cooling Methods 0.000 claims abstract description 20
- 239000002994 raw material Substances 0.000 claims abstract description 9
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 5
- 229910052715 tantalum Inorganic materials 0.000 claims abstract description 5
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 5
- 238000010792 warming Methods 0.000 claims description 27
- 238000009413 insulation Methods 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 9
- 239000012071 phase Substances 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 238000000498 ball milling Methods 0.000 claims description 2
- 238000010304 firing Methods 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 8
- FUJCRWPEOMXPAD-UHFFFAOYSA-N Li2O Inorganic materials [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 abstract description 3
- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 abstract description 3
- 229910002096 lithium permanganate Inorganic materials 0.000 abstract 1
- 238000004321 preservation Methods 0.000 abstract 1
- 238000001778 solid-state sintering Methods 0.000 abstract 1
- 229910001416 lithium ion Inorganic materials 0.000 description 33
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 24
- 230000005518 electrochemistry Effects 0.000 description 17
- 229910052799 carbon Inorganic materials 0.000 description 16
- 239000007774 positive electrode material Substances 0.000 description 14
- 239000000463 material Substances 0.000 description 12
- 229920000642 polymer Polymers 0.000 description 11
- 229910052596 spinel Inorganic materials 0.000 description 11
- 239000011029 spinel Substances 0.000 description 11
- 210000004027 cell Anatomy 0.000 description 8
- 238000011160 research Methods 0.000 description 8
- 230000002441 reversible effect Effects 0.000 description 8
- 230000014759 maintenance of location Effects 0.000 description 7
- 238000000227 grinding Methods 0.000 description 6
- 125000006850 spacer group Chemical group 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000008151 electrolyte solution Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 3
- 229910013457 LiZrO Inorganic materials 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 2
- 229910015645 LiMn Inorganic materials 0.000 description 2
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000011712 cell development Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 229940116007 ferrous phosphate Drugs 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910000155 iron(II) phosphate Inorganic materials 0.000 description 2
- SDEKDNPYZOERBP-UHFFFAOYSA-H iron(ii) phosphate Chemical compound [Fe+2].[Fe+2].[Fe+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O SDEKDNPYZOERBP-UHFFFAOYSA-H 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 229910021382 natural graphite Inorganic materials 0.000 description 2
- -1 nickel metal hydride Chemical class 0.000 description 2
- 238000012827 research and development Methods 0.000 description 2
- 239000007784 solid electrolyte Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000002841 Lewis acid Substances 0.000 description 1
- 239000002879 Lewis base Substances 0.000 description 1
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 1
- 229910015243 LiMg Inorganic materials 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- 229910017704 MH-Ni Inorganic materials 0.000 description 1
- 229910017739 MH—Ni Inorganic materials 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 235000006708 antioxidants Nutrition 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 239000011244 liquid electrolyte Substances 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000035800 maturation Effects 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910052987 metal hydride Inorganic materials 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 150000002891 organic anions Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000007614 solvation Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Classifications
-
- 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 relates to the anode material of a lithium battery. The general formula is LiMNO4, wherein, the M is Mg or Ca; the N is Ta, Nb or V. A method of high-temperature solid state sintering of the invention comprises the following steps: Li2O, MO and N2O5 are taken as raw materials; the M is Mg or Ca; the N is Ta, Nb or V; Li2O, MO and N2O5 of which the purity is 99.99 percent are fully mixed by a molar ratio of 1:2:1 and then ball milled in a ball mill; particle diameter of the powder is 1-2 micrometers; the powder is parched for 4 plus or minus 2 hours under a temperature of 200 DEGC and is planished tablet to be sintered in a high-temperature sintering furnace. The temperature of the furnace is raised to 1000 plus or minus 50 DEG C from the room temperature and is preserved for 8-20 hours; furnace cooling is carried out and the powder tablet is taken out to be crashed until the particle diameter is 0.8-1.6 micrometers; after evenly grinded and planished tablet, the powder is put into the high-temperature sintering furnace for the third time and the temperature is raised to 1400 plus or minus 50 DEG C from the room temperature; the furnace cooling is carried out after heat preservation for 25-36 hours; then the powder tablet is taken out to be crashed until the particle diameter is 0.5-1.2 micrometers.
Description
Technical field
The present invention relates to the positive electrode material of lithium cell.Especially LiMgTaO
4, LiMgVO
4, LiMgNbO
4, LiCaTaO
4, LiCaVO
4And LiCaNbO
4Oxide anode material.
Background technology
Since lithium ion battery is produced in Sony corporation of Japan nineteen ninety commercialization, lithium ion battery because the energy density height, have extended cycle life, series of advantages such as open circuit voltage height, safety non-pollution, cause the attention of domestic and international battery industry more and more, its research and development and production also are the hot topics of battery industry.At present, lithium ion battery divides two big classes: liquid lithium ionic cell and polymer Li-ion battery.
In order to make polymer Li-ion battery reach large-scale commercial, still need and solve following subject matter: a. and need develop sparking voltage height, capacity is big, charge and discharge circulation life is long positive electrode material, this material needs with ionogen electric preferably consistency is arranged, to reduce contact resistance; B. need develop dendrite, the long negative material of charge and discharge circulation life do not take place; C. need develop the polymer dielectric of high conductivity, study more polyethers solid electrolyte at present after mixing, electric conductivity is still lower, and the internal resistance of battery is big, discharging current is little.
The high-energy-density of poly-lithium battery, miniaturization, slimming, lightweight, high security, long circulation life and cheaply characteristics meet requirement portable, mobile product, therefore in following 2-3, the share that replaces lithium ion battery market will reach 50%.The optimal power supply solution that is called as the 21 century mobile equipment.Polymer Li-ion battery is the battery product of new generation after Cd-Ni, MH-Ni, liquid lithium ionic cell.Japan Institute ofInformationTechnology, the report of Ltd. is estimated: to the end of the year 2002, global liquid lithium battery production is 7.11 hundred million, and " polymkeric substance " lithium cell output is 5,000 ten thousand, has increased by 29% and 119% respectively than the calendar year 2001.The major cause that increases has 3 points: in mobile phone, lithium cell is replacing nickel metal hydride battery comprehensively, and the use of two batteries of a machine and the many batteries of a machine increases; Continuing to increase of the demand of the lithium cell in laptop computer and the pick up camera; The quick expansion of digital camera market.
Polymer Li-ion battery is from application point, and outlet is broad more.Battery can be deacclimatized the dimensional requirement of consumer on one's own initiative, rather than has only standardized specification selective; Pollutions such as no soda acid and lead, mercury are the environmental protection batteries of advocating the new millennium in its structure of polymer Li-ion battery and the production process.Therefore, battery research and production unit have been attracted since autohemagglutination compound lithium ion battery comes out strongly.Come into the market soon, technology, technology are just in accelerated development and maturation.Its industrialization prospect is very tempting.The technological core of polymer Li-ion battery is to adopt polymeric matrix as electrode and electrolytical skeleton structure, and the liquid electrolyte molecule is fixed therein and forms apparent dry state, and electrode and ionogen inside have macroion electroconductibility.The gordian technique of polymer Li-ion battery is the preparation polymer dielectric.Polymer dielectric is called polymer solid electrolyte (SPE) again, and it not only needs high ionic conductance, and requires to have suitable physical strength, snappiness, pore structure and chemistry and electrochemical stability etc.The ideal lithium cell electrolyte need satisfy following requirement: macroion electroconductibility, anti-oxidant, thermally-stabilised, nontoxic, environment can be accepted, expense is rationally and be easy to get when using in a large number.
Anode material for lithium-ion batteries is the key of limiting lithium ion cell development always, compares with negative material, and positive electrode material energy density and power density are low, and also is the major cause that causes lithium ion battery security hidden danger.The development of positive electrode material mainly embodies a concentrated reflection of seeks high-energy-density, high power density, environmental friendliness and low-cost electrode materials.Most study be LiMn
2O
4And LiCoO
2The thermostability of lithium manganate having spinel structure is approved by consistent.Research to its high-temperature behavior mainly concentrates on bulk phase-doped and finishing.Korea S Y.J.kang etc. has studied the lithium manganate having spinel structure that Al replaces, and the stability after mixing under 55 ℃ is greatly enhanced, and its specific capacity is about 105mAh/g.Adopting colloidal sol--gel method is maximum in the research that spinel surface clad oxide compound improves aspect the high-temperature behavior.The metal oxide that coats has TiO
2, Al
2O
3, SiO
2, LiZrO
2Deng.U.S. C.Jhonson etc. has investigated ZrO
2And LiZrO
2High-temperature behavior research after the finishing, LiZrO
2The LiMn2O4 of modifying has shown under 50 ℃ and has compared ZrO
2The LiMn2O4 of modifying has better cycle performance, and circulating, specific capacity decays to 110mAh/g from 115mAh/g after 30 times.Research LiCoO
2Report concentrate on: at its surface clad oxide or composite metal oxide, improve its end of charge voltage to more than the 45V, improve its discharge capacity with this.
Positive-material lithium manganate is as outside (Chinese patent application number is 200410044225.3 lithium ion accumulator positive electrode active material lithium manganate having spinel structure) and the cobalt acid lithium, and other is as Chinese patent application number 200410039176 lithium ferrous phosphate as anode material of lithium ion battery and 200610106983.2 1 kinds of ferrous phosphate doping lithium anode materials.The temperature performance of positive electrode material LiFePO 4 of lithium is fine, but electrical capacity is not high relatively.
The negative material of business-like lithium ion battery is graphitized carbon normally, and its theoretical capacity is 372mAh/g, mainly is that it is carried out deep research at present, especially to the formation mechanism of SEI film and the research of composition.
Electrolytic solution plays between the positive and negative electrode of lithium ion battery carries Li
+Effect, the consistency of electrolytic solution and electrode directly influences the performance of battery, the research and development of electrolytic solution are extremely important to the performance of lithium ion battery and development.Still round seeking big organic anion, because anion is more big, solvation is more strong, more is conducive to shield Li in the research of electric conducting lithium salt
+, Li so
+Be easier to migration.Introduce big neutral molecule as being the Lewis acid of central atom with B, C, N, Al, P etc. in electrolytic solution, it and fluoride anion class Lewis base strong effect help breaking Li
+With anionic effect, help Li
+Migration.At present, anode material for lithium-ion batteries is still the key of limiting lithium ion cell development.Do not see yet at present LiMgTaO is arranged
4, LiMgVO
4, LiMgNbO
4, LiCaTaO
4, LiCaVO
4And LiCaNbO
4Composite oxides are done disclosing of anode material for lithium-ion batteries.
Summary of the invention
The present invention seeks to: propose a kind of anode material for lithium-ion batteries.Especially a kind of LiMg and LiCa oxide material for mixing overcomes the deficiency of the first electrochemical capacity of traditional positive electrode or cycle characteristics, seeks a kind of energy and substitutes LiMn
2O
4Positive electrode.
Technical scheme of the present invention is: anode material for lithium-ion batteries, its general formula is LiMNO
4, wherein M is Mg or Ca, N is Ta, Nb or V, i.e. LiMgTaO
4, LiMgVO
4, LiMgNbO
4, LiCaTaO
4, LiCaVO
4Or LiCaNbO
4, Mg and Ca the two can to embody the crystalline network of constituent material identical.The present invention proposes a kind of material of spinel type.
The high temperature solid-phase sintering production method of positive electrode of the present invention: with Li
2O, MO and N
2O
5Being raw material (M is Mg or Ca, and N is Ta, Nb or V), is 99.99% Li with purity
2O, MO and N
2O
5Fully mix by 1: 2: 1 mol ratio, obtain respectively LiMgTaO
4, LiMgNbO
4, LiMgVO
4, LiCaTaO
4, LiCaVO
4Or LiCaNbO
4, ball milling in ball mill then, the particle diameter of powder reaches the 1-2 micron.At LiMgTaO
4, LiMgNbO
4, LiCaTaO
4, or LiCaNbO
4The condition of heating be: 200 ℃ of oven dry 4 ± 2 hours, compacting was in flakes put into high temperature sintering furnace and is fired.Furnace temperature is warming up to 1000 ± 50 ℃ by room temperature, insulation 8-20h, with the stove cooling, it is the 0.8-1.6 micron that the pressed powder taking-up is crushed to particle diameter, grind evenly, be compressed into tablets and again put into high temperature sintering furnace and be warming up to 1000 ± 50 ℃ by room temperature, insulation 8-20h cools off with stove, grind evenly, put into for the third time high temperature sintering furnace after being compressed into tablets and be warming up to 1400 ± 50 ℃ by room temperature, with the stove cooling, it is the 0.5-1.2 micron that the taking-up pressed powder is crushed to particle diameter behind the insulation 25-36h.At LiMgVO
4Or LiCaVO
4The condition of heating be: 200 ℃ of oven dry 4 ± 2 hours, compacting was in flakes put into high temperature sintering furnace and is fired.Furnace temperature is warming up to 650 ± 20 ℃ by room temperature, insulation 8-20h, with the stove cooling, it is the 0.8-1.6 micron that the pressed powder taking-up is crushed to particle diameter, grind evenly, be compressed into tablets and again put into high temperature sintering furnace and be warming up to 650 ± 20 ℃ by room temperature, insulation 8-20h cools off with stove, grind evenly, put into for the third time high temperature sintering furnace after being compressed into tablets and be warming up to 1100 ± 20 ℃ by room temperature, with the stove cooling, it is the 0.5-1.2 micron that the taking-up pressed powder is crushed to particle diameter behind the insulation 25-36h.Prepare successfully purified single-phase LiMgTaO at last
4, LiMgNbO
4, LiMgVO
4, LiCaTaO
4, LiCaVO
4Or LiCaNbO
4Anode material of lithium battery.
Positive electrode material of the present invention can prepare lithium ion battery with negative material natural graphite coupling, electrochemistry capacitance can reach more than the 125mAh/g, reversible cycle electrochemical capacity is 115 ± 3mAh/g first, preliminary test is represented, keep more than 80% of initial discharge electrochemistry capacitance after the charge and discharge cycles 100 times, promptly the electrochemical capability retention is 80%.Charge and discharge cycles keeps more than 67% of initial discharge electrochemistry capacitance 300 times afterwards.The condition that temperature is used is also very wide.Especially LiCaVO
4And LiMgVO
4Electrochemistry capacitance bigger.
Embodiment
1.LiMgTaO
4
Method with high temperature solid-phase sintering prepares LiMgTaO
4Anode material of lithium battery.With Li
2O, MgO and Ta
2O
5Being raw material, is 99.99% Li with purity
2O, MgO and Ta
2O
5Fully mix by 1: 2: 1 mol ratio, then in grinding in ball grinder, the particle diameter of powder reaches the 1-2 micron, 200 ℃ of oven dry 4 hours, is compressed into tablets, and puts into high temperature sintering furnace and fires.Furnace temperature is warming up to 1000 ℃ by 20 ℃, be incubated to 10h, with the stove cooling, it is the 0.8-1.6 micron that the pressed powder taking-up is crushed to particle diameter, grind evenly, be compressed into tablets and again put into high temperature sintering furnace and be warming up to 1000 ℃ by 20 ℃, be incubated to 10h, cool off with stove, grind evenly, put into for the third time high temperature sintering furnace after being compressed into tablets and be warming up to 1400 ℃ by 20 ℃, with the stove cooling, it is the 0.5-1.2 micron that the taking-up pressed powder is crushed to particle diameter behind the insulation 30h.Finally prepare successfully purified single-phase LiMgTaO
4Anode material of lithium battery.The result shows LiMgTaO
4Be spinel structure, belong to isometric system, spacer is Fd3m.
By LiMgTaO
4The lithium ion battery of forming as positive electrode material electrochemical capacity first is 128 ± 4mAh/g, reversible cycle electrochemical capacity is 115 ± 3mAh/g first, keep more than 81% of initial discharge electrochemistry capacitance after the charge and discharge cycles 100 times, promptly the electrochemical capability retention is 81%.Charge and discharge cycles keeps more than 72% of initial discharge electrochemistry capacitance 300 times afterwards.
2.LiMgVO
4
Method with high temperature solid-phase sintering prepares LiMgVO
4Anode material of lithium battery.With Li
2O, MgO and V
2O
5Being raw material, is 99.99% Li with purity
2O, MgO and V
2O
5Fully mix by 1: 2: 1 mol ratio, then in grinding in ball grinder, the particle diameter of powder reaches the 1-2 micron, 200 ℃ of oven dry 4 hours, is compressed into tablets, and puts into high temperature sintering furnace and fires.Furnace temperature is warming up to 650 ℃ by 20 ℃, be incubated to 10h, with the stove cooling, it is the 0.8-1.6 micron that the pressed powder taking-up is crushed to particle diameter, grind evenly, be compressed into tablets and again put into high temperature sintering furnace and be warming up to 650 ℃ by 20 ℃, be incubated to 10h, cool off with stove, grind evenly, put into for the third time high temperature sintering furnace after being compressed into tablets and be warming up to 1100 ℃ by 20 ℃, with the stove cooling, it is the 0.5-1.2 micron that the taking-up pressed powder is crushed to particle diameter behind the insulation 25h.Finally prepare successfully purified single-phase LiMgVO
4Anode material of lithium battery.The result shows LiMgVO
4Be spinel structure, belong to isometric system, spacer is Fd3m.
By LiMgVO
4The lithium ion battery of forming as positive electrode material electrochemical capacity first is 136 ± 3mAh/g, reversible cycle electrochemical capacity is 120 ± 4mAh/g first, keep more than 85% of initial discharge electrochemistry capacitance after the charge and discharge cycles 100 times, promptly the electrochemical capability retention is 85%.Charge and discharge cycles keeps more than 73% of initial discharge electrochemistry capacitance 300 times afterwards.
3.LiMgNbO
4
Method with high temperature solid-phase sintering prepares LiMgNbO
4Anode material of lithium battery.With Li
2O, MgO and Nb
2O
5Being raw material, is 99.99% Li2O, MgO and Nb with purity
2O
5Fully mix by 1: 2: 1 mol ratio, then in grinding in ball grinder, the particle diameter of powder reaches the 1-2 micron, 200 ℃ of oven dry 4 hours, is compressed into tablets, and puts into high temperature sintering furnace and fires.Furnace temperature is warming up to 1000 ℃ by 20 ℃, be incubated to 10h, with the stove cooling, it is the 0.8-1.6 micron that the pressed powder taking-up is crushed to particle diameter, grind evenly, be compressed into tablets and again put into high temperature sintering furnace and be warming up to 1000 ℃ by 20 ℃, be incubated to 10h, cool off with stove, grind evenly, put into for the third time high temperature sintering furnace after being compressed into tablets and be warming up to 1400 ℃ by 20 ℃, with the stove cooling, it is the 0.5-1.2 micron that the taking-up pressed powder is crushed to particle diameter behind the insulation 30h.Finally prepare successfully purified single-phase LiMgNbO
4Anode material of lithium battery.
The result shows LiMgNbO
4Be spinel structure, belong to isometric system, spacer is Fd3m.
By LiMgNbO
4The lithium ion battery of forming as positive electrode material electrochemical capacity first is 125 ± 3mAh/g, reversible cycle electrochemical capacity is 116 ± 2mAh/g first, keep more than 83% of initial discharge electrochemistry capacitance after the charge and discharge cycles 100 times, promptly the electrochemical capability retention is 83%.Charge and discharge cycles keeps more than 70% of initial discharge electrochemistry capacitance 300 times afterwards.
4.LiCaTaO
4
Method with high temperature solid-phase sintering prepares LiCaTaO
4Anode material of lithium battery.With Li
2O, CaO and Ta
2O
5Being raw material, is 99.99% Li with purity
2O, CaO and Ta
2O
5Fully mix by 1: 2: 1 mol ratio, then in grinding in ball grinder, the particle diameter of powder reaches the 1-2 micron, 200 ℃ of oven dry 4 hours, is compressed into tablets, and puts into high temperature sintering furnace and fires.Furnace temperature is warming up to 1000 ℃ by 20 ℃, be incubated to 10h, with the stove cooling, it is the 0.8-1.6 micron that the pressed powder taking-up is crushed to particle diameter, grind evenly, be compressed into tablets and again put into high temperature sintering furnace and be warming up to 1000 ℃ by 20 ℃, be incubated to 10h, cool off with stove, grind evenly, put into for the third time high temperature sintering furnace after being compressed into tablets and be warming up to 1400 ℃ by 20 ℃, with the stove cooling, it is the 0.5-1.2 micron that the taking-up pressed powder is crushed to particle diameter behind the insulation 30h.Finally prepare successfully purified single-phase LiCaTaO
4Anode material of lithium battery.
The result shows LiCaTaO
4Be spinel structure, belong to isometric system, spacer is Fd3m.
By LiCaTaO
4The lithium ion battery of forming as positive electrode material electrochemical capacity first is 128 ± 3mAh/g, reversible cycle electrochemical capacity is 120 ± 2mAh/g first, keep more than 80% of initial discharge electrochemistry capacitance after the charge and discharge cycles 100 times, promptly the electrochemical capability retention is 80%.Charge and discharge cycles keeps more than 67% of initial discharge electrochemistry capacitance 300 times afterwards.
5.LiCaVO
4
Method with high temperature solid-phase sintering prepares LiCaVO
4Anode material of lithium battery.With Li
2O, CaO and V
2O
5Being raw material, is 99.99% Li with purity
2O, CaO and V
2O
5Fully mix by 1: 2: 1 mol ratio, then in grinding in ball grinder, the particle diameter of powder reaches the 1-2 micron, 200 ℃ of oven dry 4 hours, is compressed into tablets, and puts into high temperature sintering furnace and fires.Furnace temperature is warming up to 650 ℃ by 20 ℃, be incubated to 10h, with the stove cooling, it is the 0.8-1.6 micron that the pressed powder taking-up is crushed to particle diameter, grind evenly, be compressed into tablets and again put into high temperature sintering furnace and be warming up to 650 ℃ by 20 ℃, be incubated to 10h, cool off with stove, grind evenly, put into for the third time high temperature sintering furnace after being compressed into tablets and be warming up to 1100 ℃ by 20 ℃, with the stove cooling, it is the 0.5-1.2 micron that the taking-up pressed powder is crushed to particle diameter behind the insulation 25h.Finally prepare successfully purified single-phase LiCaVO
4Anode material of lithium battery.
The result shows LiCaVO
4Be spinel structure, belong to isometric system, spacer is Fd3m.
By LiCaVO
4The lithium ion battery of forming as positive electrode material electrochemical capacity first is 138 ± 3mAh/g, reversible cycle electrochemical capacity is 124 ± 3mAh/g first, keep more than 87% of initial discharge electrochemistry capacitance after the charge and discharge cycles 100 times, promptly the electrochemical capability retention is 87%.Charge and discharge cycles keeps more than 76% of initial discharge electrochemistry capacitance 300 times afterwards.
6.LiCaNbO
4
Method with high temperature solid-phase sintering prepares LiCaNbO
4Anode material of lithium battery.With Li
2O, CaO and Nb
2O
5Being raw material, is 99.99% Li with purity
2O, CaO and Nb
2O
5Fully mix by 1: 2: 1 mol ratio, then in grinding in ball grinder, the particle diameter of powder reaches the 1-2 micron, 200 ℃ of oven dry 4 hours, is compressed into tablets, and puts into high temperature sintering furnace and fires.Furnace temperature is warming up to 1000 ℃ by 20 ℃, be incubated to 10h, with the stove cooling, it is the 0.8-1.6 micron that the pressed powder taking-up is crushed to particle diameter, grind evenly, be compressed into tablets and again put into high temperature sintering furnace and be warming up to 1000 ℃ by 20 ℃, be incubated to 10h, cool off with stove, grind evenly, put into for the third time high temperature sintering furnace after being compressed into tablets and be warming up to 1380 ℃ by 20 ℃, with the stove cooling, it is the 0.5-1.2 micron that the taking-up pressed powder is crushed to particle diameter behind the insulation 30h.Finally prepare successfully purified single-phase LiCaNbO
4Anode material of lithium battery.
The result shows LiCaNbO
4Be spinel structure, belong to isometric system, spacer is Fd3m.
By LiCaNbO
4The lithium ion battery of forming as positive electrode material electrochemical capacity first is 130 ± 4mAh/g, reversible cycle electrochemical capacity is 123 ± 4mAh/g first, keep more than 82% of initial discharge electrochemistry capacitance after the charge and discharge cycles 100 times, promptly the electrochemical capability retention is 82%.Charge and discharge cycles keeps more than 71% of initial discharge electrochemistry capacitance 300 times afterwards.
The negative material of the present invention coupling adopts carbon (natural graphite), has good reversibility, capacity is big and discharge platform the is low characteristics of discharging and recharging.The electric weight of the active substance charge or discharge that electrochemistry capacitance is often referred to unit mass at utmost the time generally represented with mAh/g.The charging mechanism of graphite-like carbon is that the lithium ion reversible is embedded into graphite layers, and corresponding electrochemistry capacitance is 372mAh/g.The electrode potential of desirable negative material should approach with lithium metal, changes not quite with the embedded quantity of lithium is different.The electropotential of graphite from 0.4V to 0.0V (with respect to Li
+/ change between Li), be the negative material that relatively is fit to.
Electrolytical effect is to form good ionic conduction passage between the inside battery positive and negative electrode.Electrolyte among the present invention is 1mol L
-1LiPF
6The mixing solutions of diethyl carbonate (DEC) and NSC 11801 (EC) (mol ratio of DEC and EC is 1: 1).Barrier film is U.S. Celgard 2400 films.
Claims (1)
1. the high temperature solid-phase sintering production method of anode material of lithium battery is characterized in that with Li
2O, MO and N
2O
5Be raw material, M is Ca, and N is Ta, Nb or V, is 99.99% Li with purity
2O, MO and N
2O
5Fully mix by 1: 2: 1 mol ratio, ball milling in ball mill then, the particle diameter of powder reaches the 1-2 micron, 200 ℃ of oven dry 4 ± 2 hours, is compressed into tablets, and puts into high temperature sintering furnace and fires; When firing furnace temperature is warming up to 1000 ± 50 ℃ by room temperature, insulation 8-20h, with the stove cooling, it is the 0.8-1.6 micron that the pressed powder taking-up is crushed to particle diameter, grind evenly, be compressed into tablets and again put into high temperature sintering furnace and be warming up to 1000 ± 50 ℃ by room temperature, insulation 8-20h cools off with stove, grind evenly, put into for the third time high temperature sintering furnace after being compressed into tablets and be warming up to 1400 ± 50 ℃ by room temperature, with the stove cooling, it is the 0.5-1.2 micron that the taking-up pressed powder is crushed to particle diameter behind the insulation 25-36h; Prepare pure single-phase LiCaTaO
4, LiCaVO
4Or LiCaNbO
4Anode material of lithium battery.
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