CN104795539B - A kind of liquid phase synthesis Cu2+,Fe3+Sheet of adulterating fluorination bismuth anode material for lithium-ion batteries and preparation method thereof - Google Patents
A kind of liquid phase synthesis Cu2+,Fe3+Sheet of adulterating fluorination bismuth anode material for lithium-ion batteries and preparation method thereof Download PDFInfo
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- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 229910052797 bismuth Inorganic materials 0.000 title claims abstract description 29
- 238000003682 fluorination reaction Methods 0.000 title claims abstract description 25
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 23
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000007791 liquid phase Substances 0.000 title claims abstract description 15
- 239000010405 anode material Substances 0.000 title claims abstract description 10
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 9
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 8
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 19
- 239000007864 aqueous solution Substances 0.000 claims description 53
- 239000000243 solution Substances 0.000 claims description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 33
- 239000000203 mixture Substances 0.000 claims description 24
- 238000003756 stirring Methods 0.000 claims description 16
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 9
- 239000004809 Teflon Substances 0.000 claims description 8
- 229920006362 Teflon® Polymers 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 230000002572 peristaltic effect Effects 0.000 claims description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 7
- 239000010949 copper Substances 0.000 claims description 7
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical class [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 7
- 230000001186 cumulative effect Effects 0.000 claims description 7
- PPNKDDZCLDMRHS-UHFFFAOYSA-N dinitrooxybismuthanyl nitrate Chemical class [Bi+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PPNKDDZCLDMRHS-UHFFFAOYSA-N 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 150000002823 nitrates Chemical class 0.000 claims description 6
- QXNVGIXVLWOKEQ-UHFFFAOYSA-N Disodium Chemical compound [Na][Na] QXNVGIXVLWOKEQ-UHFFFAOYSA-N 0.000 claims description 5
- CCUWGJDGLACFQT-UHFFFAOYSA-N 2,2,3,3,4,4-hexafluoropentanedioic acid Chemical compound OC(=O)C(F)(F)C(F)(F)C(F)(F)C(O)=O CCUWGJDGLACFQT-UHFFFAOYSA-N 0.000 claims description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 4
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 4
- MJJJJEUEZVGFLW-UHFFFAOYSA-N 2-dodecyl-2-sulfobutanedioic acid Chemical group CCCCCCCCCCCCC(S(O)(=O)=O)(C(O)=O)CC(O)=O MJJJJEUEZVGFLW-UHFFFAOYSA-N 0.000 claims description 3
- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical compound OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 claims description 3
- 239000013078 crystal Substances 0.000 claims description 3
- GWTCIAGIKURVBJ-UHFFFAOYSA-L dipotassium;dodecyl phosphate Chemical compound [K+].[K+].CCCCCCCCCCCCOP([O-])([O-])=O GWTCIAGIKURVBJ-UHFFFAOYSA-L 0.000 claims description 3
- ZWBAMYVPMDSJGQ-UHFFFAOYSA-N perfluoroheptanoic acid Chemical compound OC(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F ZWBAMYVPMDSJGQ-UHFFFAOYSA-N 0.000 claims description 3
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- OZECDDHOAMNMQI-UHFFFAOYSA-H cerium(3+);trisulfate Chemical compound [Ce+3].[Ce+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O OZECDDHOAMNMQI-UHFFFAOYSA-H 0.000 claims description 2
- 238000002425 crystallisation Methods 0.000 claims description 2
- 230000008025 crystallization Effects 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 2
- HHLJUSLZGFYWKW-UHFFFAOYSA-N triethanolamine hydrochloride Chemical compound Cl.OCCN(CCO)CCO HHLJUSLZGFYWKW-UHFFFAOYSA-N 0.000 claims description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims 2
- 150000001408 amides Chemical class 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 23
- 238000000034 method Methods 0.000 abstract description 16
- 230000008569 process Effects 0.000 abstract description 7
- 239000000047 product Substances 0.000 abstract description 6
- 239000000126 substance Substances 0.000 abstract description 5
- 150000003839 salts Chemical class 0.000 abstract description 3
- 238000007086 side reaction Methods 0.000 abstract description 3
- 239000007795 chemical reaction product Substances 0.000 abstract description 2
- 238000013461 design Methods 0.000 abstract description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 7
- 229910052744 lithium Inorganic materials 0.000 description 7
- 239000000428 dust Substances 0.000 description 5
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen(.) Chemical compound [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 5
- 230000004087 circulation Effects 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 235000013162 Cocos nucifera Nutrition 0.000 description 3
- 244000060011 Cocos nucifera Species 0.000 description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 3
- -1 Triethanolammonium chlorides Chemical class 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 235000014113 dietary fatty acids Nutrition 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229930195729 fatty acid Natural products 0.000 description 3
- 239000000194 fatty acid Substances 0.000 description 3
- 150000004665 fatty acids Chemical class 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 2
- 229910007086 Li1+xV3O8 Inorganic materials 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 2
- JYPVGDJNZGAXBB-UHFFFAOYSA-N bismuth lithium Chemical compound [Li].[Bi] JYPVGDJNZGAXBB-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- YMGUBTXCNDTFJI-UHFFFAOYSA-N cyclopropanecarboxylic acid Chemical compound OC(=O)C1CC1 YMGUBTXCNDTFJI-UHFFFAOYSA-N 0.000 description 2
- 238000009831 deintercalation Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 238000012827 research and development Methods 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 1
- 241000446313 Lamella Species 0.000 description 1
- 229910032387 LiCoO2 Inorganic materials 0.000 description 1
- 229910010710 LiFePO Inorganic materials 0.000 description 1
- 229910052493 LiFePO4 Inorganic materials 0.000 description 1
- 229910002993 LiMnO2 Inorganic materials 0.000 description 1
- 229910013292 LiNiO Inorganic materials 0.000 description 1
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 description 1
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 229920002892 amber Polymers 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 150000002169 ethanolamines Chemical class 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 229920000831 ionic polymer Polymers 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- ZAUUZASCMSWKGX-UHFFFAOYSA-N manganese nickel Chemical compound [Mn].[Ni] ZAUUZASCMSWKGX-UHFFFAOYSA-N 0.000 description 1
- 230000010534 mechanism of action Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- ZDQYSKICYIVCPN-UHFFFAOYSA-L sodium succinate (anhydrous) Chemical compound [Na+].[Na+].[O-]C(=O)CCC([O-])=O ZDQYSKICYIVCPN-UHFFFAOYSA-L 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 1
- 238000006277 sulfonation reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—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
- H01M4/582—Halogenides
-
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/626—Metals
-
- 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
A kind of liquid phase synthesis Cu2+, Fe3+Sheet of adulterating fluorination bismuth anode material for lithium-ion batteries and preparation method thereof, this method design by process conditions and is introduced a variety of auxiliary agents and prepares sheet fluorination bismuth by liquid phase reactor, and passes through Cu2+, Fe3+Doping improves the discharge platform voltage and capacity holding capacity of material, and the fluorination bismuth material is used with more than 200mAh.g as anode material for lithium-ion batteries‑1Specific capacity.This method equipment requirement is low, and product purity is high, is avoided that in liquid phase reactor generation is fluorinated the side reaction products such as a variety of double salt of bismuth and with excellent chemical property.
Description
Technical field
The present invention relates to a kind of electric positive electrode manufacture method technical field of high power capacity fluorination bismuth complex lithium.
Background technology
Lithium rechargeable battery has volume, weight energy higher than high, voltage, low self-discharge rate, memory-less effect, circulation
Long lifespan, power density height etc. definitely advantage, had more than at present in global portable power source market 30,000,000,000 dollar/year shares and with
Speed more than 10% gradually increases.Particularly in recent years, petering out with fossil energy, solar energy, wind energy, biomass
The new energy such as energy are increasingly becoming the alternative of traditional energy, and wherein wind energy, solar energy has intermittence, to meet lasting electricity
Power supply needs to use substantial amounts of energy-storage battery simultaneously；The urban air-quality problem that vehicle exhaust is brought is increasingly serious, electronic
Very urgent stage has been arrived in vigorously advocating and developing for car (EV) or hybrid electric vehicle (HEV)；These demands are provided
Lithium ion battery explosive growth point, while also the performance to lithium ion battery proposes higher requirement.
The raising of the capacity of anode material for lithium-ion batteries is the primary goal of scientific and technical personnel's research, high power capacity positive electrode
Research and development can to alleviate current Li-ion batteries piles volume big, heavy weight, price high-leveled and difficult to meet high power consumption and high-power equipment
The situation needed.But since lithium ion battery commercialization in 1991, the actual specific capacity of positive electrode is hovered all the time
Between 100-180mAh/g, the low bottleneck for having become lifting lithium ion battery specific energy of positive electrode specific capacity.It is commercial at present
The most commonly used practical positive electrode of lithium ion battery be LiCoO2, the theoretical specific capacity of cobalt acid lithium is 274mAh/g, and
Actual specific capacity is between 130-140mAh/g, and cobalt is strategic materials, expensive and have larger toxicity.Therefore in recent years
Come, the researcher of countries in the world is directed to the research and development of Olivine-type Cathode Material in Li-ion Batteries always, to current, screening
Up to tens of kinds of the lithium ion cell positive gone out, but really have potential commercial applications prospect or be already present in the market just
Pole material is really very few.Such as lithium manganate having spinel structure LiMn2O4, its cost is relatively low, is easier to prepare, security performance
It is relatively good, but capacity is relatively low, theoretical capacity is 148mAh/g, and actual capacity is in 100-120mAh/g, and the material capacity
Circulate holding capacity it is not good, under high temperature capacity attenuation quickly, Mn3+John-Teller effects and dissolving in the electrolyte it is long
Researcher has been annoying since phase.The LiNiO of layer structure2And LiMnO2Although there is larger theoretical specific capacity, it is respectively
275mAh/g and 285mAh/g, but they prepare extremely difficult, heat endurance is poor, and cyclicity is very poor, and capacity attenuation is quickly.And
Progressively commercialized LiFePO4 LiFePO at present4Cost is low, heat endurance is good, environment-friendly, but its theoretical capacity
About there was only 170mAh/g, and actual capacity is in 140mAh/g or so [Chun SY, Bloking J T, Chiang Y M, Nature
Materials, 2002,1：123-128.].The positive electrode more than 200mAh/g specific capacities for having market prospects at present only has vanadium
Sour lithium Li1+xV3O8, Li1+xV3O8Material can have possesses even close to 300mAh/g capacity, but its discharge average voltage it is relatively low and
And in production process barium oxide often toxicity is larger.High lithium is than on positive electrode in recent years, particularly manganese base manganese-nickel binary and
The high lithium of manganese base manganese-nickel-cobalt ternary solid solution system is steady with the Capacity Ratio more than 200mAh/g, higher heat than positive electrode
The cost of qualitative and relative moderate and paid close attention to by people, but the performance under the material high magnification is very undesirable, limitation
Its application [Young-Sik Hong, Yong Joon Park, et al., Solid State in electrokinetic cell
Ionics, 2005,176：1035-1042].
In recent years, fluoride positive electrode is because its capacity is high, the prices of raw materials are low and enter the visual field of researcher.Fluorine
The operation principle of compound material and conventional lithium ion battery positive electrode is different, traditional lithium ion cell positive and negative pole
All exist lithium ion can be embedded in or deintercalation space, and lithium ion in electrolyte it is embedded back and forth between a positive electrode and a negative electrode and
Deintercalation and " rocking chair " battery proposed as Armand etc. that discharges.And fluoride is then a kind of transition material, that is, whole
In individual discharge process, although Me has nothing in common with each other, MeFnCan occur similar following change [Badway F, Cosandey F,
Pereira N, et al., Electrodes for Li Batteries, J.Electrochem.Soc., 2003,150 (10)：
A1318-A1327.]：
nLi++MeFn+ne-→nLiF+Me0
It can discharge in this process and exceed well over 200mAh.g-1Specific capacity, thus it is high to obtain investigation of materials personnel
The attention of degree.Wherein fluorination bismuth is due to there is about 7170WhL-1Volume and capacity ratio and have big advantage.Conventional fluorine
Change the synthetic method of bismuth to be carried out with metal simple-substance with metal oxide/hydroxide or fluorine gas with hydrogen fluoride gas at high temperature
Reaction, process conditions are harsh, and equipment requirement is very high, high energy consumption, therefore price is very expensive.And liquid phase reactor prepares fluorination bismuth
Then it can not often be used because by-products content is too high as positive electrode while also lacking warp because producing many costs height of waste liquid
Ji property.Bismuth, which is fluorinated, as lithium ion secondary battery anode material also has a negative characteristic to be that its electronic conductivity is extremely low,
Therefore very high polarizing voltage can be caused in charge and discharge process.
In addition fluorination bismuth crystal formation and pattern in lattice electrons transport property influence it is very big, therefore be directly connected to lithium from
The chemical property of sub- battery such as charge/discharge rates, capacity and circulation volume holding capacity；Ion doping is a kind of effective tune
The microstructure of lattice is saved, changes the means of lattice electron and ionic transport properties, however, ion doping even polyion is assisted
Extremely complex to the mechanism of action of parent with doping, effect is often difficult to expect.
Therefore a kind of simple technique, product quality stabilization, the liquid phase synthesis fluorination bismuth with excellent electrochemical performance are developed
Preparation method is to be fluorinated the key that bismuth material is applied as secondary cell.
The content of the invention
The present invention proposes a kind of liquid phase synthesis Cu for existing background technology2+, Fe3+Adulterate sheet fluorination bismuth lithium from
Sub- cell positive material and preparation method thereof, this method is by liquid phase reactor, and the design and introducing by process conditions are a variety of
Auxiliary agent prepares sheet fluorination bismuth, and passes through Cu2+, Fe3+The discharge platform voltage and capacity that doping improves material keep energy
Power, the fluorination bismuth material is used with more than 200mAh.g as anode material for lithium-ion batteries-1Specific capacity.This method equipment
It is required that low, product purity is high, is avoided that in liquid phase reactor generation is fluorinated the side reaction products such as a variety of double salt of bismuth and with excellent
Different chemical property.
This liquid phase synthesis Cu2+, Fe3+Sheet of adulterating fluorination bismuth method for preparing anode material of lithium-ion battery, its feature
For：It is 5-15wt% bismuth nitrates, 0.1-0.3wt% copper nitrates, 0.1-0.5wt% ferric nitrates, the dilute nitre of 1-5wt% to prepare composition
Acid, 0.1-0.5wt% auxiliary agents Z1 water solution A 200-300mL, prepare ammonium fluoride, 0.1- of the composition for 15-45wt%
0.5wt% auxiliary agents Z2 aqueous solution B 200-300mL, water solution A is identical with aqueous solution B volume, ammonium fluoride in aqueous solution B
Concentration is 3 times of nitric acid bi concns in water solution A；Preparing 0.1-0.5wt% auxiliary agent Z3,0.1-0.5wt%, there is crystallization to control
The auxiliary agent Z4 of making aqueous solution C；Aqueous solution C is put into volume for 2L, internal diameter is in 15-20 centimetres of cylindrical reactor
To the 1/3-1/2 of reactor cumulative volume, aqueous solution C temperature setting is used into Teflon stir simultaneously at 40-60 DEG C
Oar is stirred with 1200rpm-1500rpm speed.Using peristaltic pump at a same speed simultaneously by water solution A and aqueous solution B pumps
Enter the ad-hoc location in reactor and until the whole pumps of the water solution A and aqueous solution B of all preparations are complete.The temperature of reactor is adjusted
Whole is 30-40 DEG C, maintains the speed of stirring constant, and reactor is placed in into the nitrogen and hydrogen that an atmospheric pressure volume ratio is 95: 5
Kept for 20-40 hours in mixed gas.Thereafter, by filtering, obtained after being dried 10-20 hours in 100-150 DEG C of drying box
Obtain Cu2+, Fe3+Sheet of adulterating fluorination bismuth.
Auxiliary agent Z1 is one kind in monoethanolamine, triethanolamine, Triethanolammonium chloride in preparation method as described above；Auxiliary agent
Z2 is mean molecule quantity in 10000-20000 polyvinyl alcohol, op-10, Tween-40；Auxiliary agent Z3 is perfluoro-heptanoic acid, 2,2- difluoro rings
One kind in third carboxylic acid, perfluoroglutaric acid；It is lauryl sulfosuccinic acid monoester disodium with the auxiliary agent Z4 that cerium sulphate crystal is acted on,
One kind in Coconut Fatty Acid Monoethanolamide sulfosuccinic acid monoesters disodium, Monododecylphosphate potassium；
The diameter of Teflon stir oar is smaller than the diameter of reactor 5 centimetres in preparation method as described above；Wriggle
It is 0.1-1mL/ minutes that pump, which conveys water solution A and aqueous solution B speed,；Ad-hoc location as described above refers to water solution A and enters anti-
The entrance and aqueous solution B for answering device enter the entrance of reactor in same plane and on using mixing paddle axle as the circle in the center of circle, and two
The line of person is by the center of circle and diameter is smaller than the diameter of agitating paddle 1 centimetre.
Fig. 1 is charging capacity, discharge capacity and the efficiency for charge-discharge figure of preceding 10 circulations of the material, voltage range
1.8V-4.0V, charging and discharging currents 0.1C.Fig. 2 is the pattern of visible sheet in the scanning electron microscope (SEM) photograph of the material, figure.
Compared with prior art, the advantage of the invention is that：This method is by liquid phase reactor, and setting by process conditions
Count and introduce a variety of auxiliary agents and prepare sheet fluorination bismuth, and pass through Cu2+, Fe3+Doping improves the discharge platform voltage of material
And capacity holding capacity, the fluorination bismuth material is used as anode material for lithium-ion batteries to be had more than 200mAh.g-1Specific volume
Amount.This method equipment requirement is low, and product purity is high, is avoided that the side reaction such as a variety of double salt of generation fluorination bismuth in liquid phase reactor
Product simultaneously has excellent chemical property.
Brief description of the drawings
Charging capacity, discharge capacity and the efficiency for charge-discharge figure of preceding 10 circulations of Fig. 1 materials, voltage range 1.8V-
4.0V, charging and discharging currents 0.1C.
The scanning electron microscope (SEM) photograph of Fig. 2 materials.
Embodiment
The present invention is described in further detail below in conjunction with embodiment.
Embodiment 1：It is 5wt% bismuth nitrates, 1wt% dust technologies, 0.1wt% copper nitrates, 0.1wt% to prepare 200mL compositions
The water solution A of ferric nitrate, 0.1wt% monoethanolamines；Prepare ammonium fluoride, 0.1wt% mean molecule quantity of the 200mL compositions for 15wt%
In the aqueous solution B of 10000-20000 polyvinyl alcohol；It is 0.1wt% perfluoro-heptanoic acids, 0.1wt% lauryl sulfonation ambers to prepare composition
The aqueous solution C of amber acid monoester disodium；Aqueous solution C is put into 2L volumes, internal diameter is extremely reaction in 15 centimetres of cylindrical reactor
At the 1/3 of device cumulative volume, by aqueous solution C temperature setting at 40 DEG C simultaneously using a diameter of 10 centimetres of Teflon stir
Oar is stirred with 1250rpm speed.Water solution A and aqueous solution B are pumped into instead simultaneously with 0.1mL/ minutes speed using peristaltic pump
Answer device and until the whole pumps of the water solution A and aqueous solution B of all preparations are complete.Water solution A enters the entrance and aqueous solution B of reactor
Entrance into reactor is in same plane and on using mixing paddle axle as the circle in the center of circle, and both lines are by the center of circle and straight
Footpath is smaller than the diameter of agitating paddle 1 centimetre.At this moment the temperature of reactor is adjusted to 30 DEG C, maintains the speed of stirring constant, will be anti-
Answer device to be placed in the nitrogen and hydrogen gas mixture that an atmospheric pressure volume ratio is 95: 5 to be kept for 20 hours.Thereafter, by filtering,
Cu is obtained after being dried 10 hours in 100 DEG C of drying box2+, Fe3+Sheet of adulterating fluorination bismuth.
Embodiment 2：It is 15wt% bismuth nitrates, 0.3wt% copper nitrates, 0.4wt% ferric nitrates, 5wt% to prepare 300mL compositions
The water solution A of dust technology, 0.5wt% Triethanolammonium chlorides；Prepare 300mL compositions average for 45wt% ammonium fluoride, 0.5wt%
Aqueous solution B of the molecular weight in 10000-20000 polyvinyl alcohol；Prepare composition be 0.5wt%2,2- difluoros cyclopropyl carboxylic acid and
The aqueous solution C of 0.5wt% Coconut Fatty Acid Monoethanolamide sulfosuccinic acid monoesters disodiums；Aqueous solution C is put into 2L volumes, internal diameter is
To at the 1/2 of reactor cumulative volume in 20 centimetres of cylindrical reactor, aqueous solution C temperature setting is used simultaneously at 60 DEG C
A diameter of 15 centimetres of Teflon stir oar is stirred with 1500rpm speed.It is same with 1mL/ minutes speed using peristaltic pump
When water solution A and aqueous solution B are pumped into reactor and until the whole pumps of water solution A and aqueous solution B of all preparations are complete.The aqueous solution
A enters the entrance of reactor and aqueous solution B enters the entrance of reactor in same plane and positioned at using mixing paddle axle as the center of circle
On circle, both lines are by the center of circle and diameter is smaller than the diameter of agitating paddle 1 centimetre.At this moment the temperature of reactor is adjusted to 40
DEG C, maintain the speed of stirring constant, reactor is placed in the nitrogen and hydrogen gas mixture that an atmospheric pressure volume ratio is 95: 5
It is middle to be kept for 40 hours.Thereafter, by filtering, Cu is obtained after being dried 20 hours in 150 DEG C of drying box2+, Fe3+Adulterate lamella
Shape is fluorinated bismuth.
Embodiment 3：Prepare 250mL composition be containing 10wt% bismuth nitrates, 0.2wt% copper nitrates, 0.3wt% ferric nitrates,
The water solution A of 3wt% dust technologies, 0.3wt% triethanolamines；Prepare ammonium fluoride, 0.3wt%op- of the 250mL compositions for 30wt%
10 aqueous solution B；It is 0.3wt% perfluoroglutaric acids and the aqueous solution C of 0.3wt% Monododecylphosphate potassium to prepare composition；
Aqueous solution C is put into 2L volumes, internal diameter in 17 centimetres of cylindrical reactor at the 2/5 of reactor cumulative volume, will be water-soluble
Liquid C temperature setting is stirred using a diameter of 12 centimetres of Teflon stir oar with 1350rpm speed simultaneously at 50 DEG C.
Water solution A and aqueous solution B are pumped into by reactor and until the water of all preparations with 0.5mL/ minutes speed simultaneously using peristaltic pump
Solution A and the whole pumps of aqueous solution B are complete.Water solution A enters the entrance of reactor and aqueous solution B enters the entrance of reactor same
One plane is simultaneously located on using mixing paddle axle as the circle in the center of circle, and both lines are by the center of circle and diameter is smaller than the diameter of agitating paddle by 1
Centimetre.At this moment the temperature of reactor is adjusted to 35 DEG C, maintains the speed of stirring constant, reactor is placed in an air laminate
Product in the nitrogen and hydrogen gas mixture for 95: 5 than being kept for 30 hours.Thereafter, by filtering, done in 120 DEG C of drying box
Cu is obtained after dry 15 hours2+, Fe3+Sheet of adulterating fluorination bismuth.
Embodiment 4：It is 7wt% bismuth nitrates, 0.1wt% copper nitrates, 0.5wt% ferric nitrates, 3wt% to prepare 260mL compositions
The water solution A of dust technology, 0.3wt% Triethanolammonium chlorides；260mL compositions are prepared to tell for 21wt% ammonium fluoride, 0.4wt%
The aqueous solution B of temperature -40；It is 0.4wt%2,2- difluoros cyclopropyl carboxylic acid and 0.4wt% Coconut Fatty Acid Monoethanolamide sulfo groups to prepare composition
The aqueous solution C of monomester succinate disodium；Aqueous solution C is put into 2L volumes, internal diameter in 18 centimetres of cylindrical reactor to anti-
At answer device cumulative volume 2/5, aqueous solution C temperature setting is stirred using a diameter of 13 centimetres of polytetrafluoroethylene (PTFE) simultaneously at 40 DEG C
Oar is mixed to stir with 1200rpm speed.Water solution A and aqueous solution B are pumped into simultaneously with 0.7mL/ minutes speed using peristaltic pump
Reactor is simultaneously until the whole pumps of the water solution A and aqueous solution B of all preparations are complete.Water solution A enter reactor entrance with it is water-soluble
Liquid B enters the entrance of reactor in same plane and on using mixing paddle axle as the circle in the center of circle, and both lines are by the center of circle
And diameter is smaller than the diameter of agitating paddle 1 centimetre.At this moment the temperature of reactor is adjusted to 35 DEG C, maintains the speed of stirring constant,
Reactor is placed in the nitrogen and hydrogen gas mixture that an atmospheric pressure volume ratio is 95: 5 and kept for 30 hours.Thereafter, pass through
Filtering, Cu is obtained after being dried 10 hours in 100 DEG C of drying box2+, Fe3+Sheet of adulterating fluorination bismuth.
Embodiment 5：It is 10wt% bismuth nitrates, 0.3wt% copper nitrates, 0.2wt% ferric nitrates, 4wt% to prepare 280mL compositions
The water solution A of dust technology, 0.3wt% triethanolamines；Prepare ammonium fluoride, 0.3wt% Tween-40 of the 280mL compositions for 30wt%
Aqueous solution B；It is the water-soluble of 0.3wt% perfluoroglutaric acids and 0.2wt% lauryl sulfosuccinic acid monoester disodiums to prepare composition
Liquid C；Aqueous solution C is put into 2L volumes, internal diameter in 20 centimetres of cylindrical reactor at the 2/5 of reactor cumulative volume, will
Aqueous solution C temperature setting is at 50 DEG C simultaneously using a diameter of 15 centimetres of Teflon stir oar with 1350rpm speed
Agitation.Water solution A and aqueous solution B were pumped into simultaneously by reactor with 0.6mL/ minutes speed using peristaltic pump and until all prepare
Water solution A and the whole pumps of aqueous solution B it is complete.Water solution A enters the entrance of reactor and the aqueous solution B entrances for entering reactor exist
Same plane is simultaneously located on using mixing paddle axle as the circle in the center of circle, and both lines are by the center of circle and diameter is smaller than the diameter of agitating paddle
1 centimetre.At this moment the temperature of reactor is adjusted to 35 DEG C, maintains the speed of stirring constant, reactor is placed in an atmospheric pressure
Kept for 30 hours in nitrogen and hydrogen gas mixture that volume ratio is 95: 5.Thereafter, by filtering, in 120 DEG C of drying box
Cu is obtained after drying 15 hours2+, Fe3+Sheet of adulterating fluorination bismuth.
Claims (2)
1. a kind of liquid phase synthesis Cu2+, Fe3+Sheet of adulterating is fluorinated the preparation method of bismuth anode material for lithium-ion batteries, its feature
It is that it is 5-15wt% bismuth nitrates, 0.1-0.3wt% copper nitrates, 0.1-0.5wt% ferric nitrates, the dilute nitre of 1-5wt% to prepare composition
Acid, 0.1-0.5wt% auxiliary agents Z1 water solution A 200-300mL, prepare ammonium fluoride, 0.1- of the composition for 15-45wt%
0.5wt% auxiliary agents Z2 aqueous solution B 200-300mL, water solution A is identical with aqueous solution B volume, ammonium fluoride in aqueous solution B
Concentration is 3 times of nitric acid bi concns in water solution A；Preparing 0.1-0.5wt% auxiliary agent Z3,0.1-0.5wt%, there is crystallization to control
The auxiliary agent Z4 of making aqueous solution C；Aqueous solution C is put into volume for 2L, internal diameter is in 15-20 centimetres of cylindrical reactor
To the 1/3-1/2 of reactor cumulative volume, aqueous solution C temperature setting is used into Teflon stir simultaneously at 40-60 DEG C
Oar is stirred with 1200rpm-1500rpm speed；Using peristaltic pump at a same speed simultaneously by water solution A and aqueous solution B pumps
Enter the ad-hoc location in reactor and until the whole pumps of the water solution A and aqueous solution B of all preparations are complete；The temperature of reactor is adjusted
Whole is 30-40 DEG C, maintains the speed of stirring constant, and reactor is placed in into the nitrogen and hydrogen that an atmospheric pressure volume ratio is 95: 5
Kept for 20-40 hours in mixed gas；Thereafter, by filtering, obtained after being dried 10-20 hours in 100-150 DEG C of drying box
Obtain Cu2+, Fe3+Sheet of adulterating fluorination bismuth；
Auxiliary agent Z1 is one kind in monoethanolamine, triethanolamine, Triethanolammonium chloride in preparation method as described above；Auxiliary agent Z2 is
Mean molecule quantity is in 10000-20000 polyvinyl alcohol, op-10, Tween-40；Auxiliary agent Z3 is perfluoro-heptanoic acid, 2,2- difluoros the third carboxylic of ring
One kind in acid, perfluoroglutaric acid；It is lauryl sulfosuccinic acid monoester disodium, cocounut oil with the auxiliary agent Z4 that cerium sulphate crystal is acted on
One kind in sour single ethanol amide sulfosuccinic acid monoesters disodium, Monododecylphosphate potassium；
The diameter of Teflon stir oar is smaller than the diameter of reactor 5 centimetres in preparation method as described above；Peristaltic pump is defeated
It is 0.1-1mL/ minutes to send water solution A and aqueous solution B speed；Ad-hoc location as described above refers to water solution A and enters reactor
Entrance and aqueous solution B enter the entrance of reactor in same plane and on using mixing paddle axle as the circle in the center of circle, both
Line is by the center of circle and diameter is smaller than the diameter of agitating paddle 1 centimetre.
2. liquid phase synthesis Cu according to claim 12+, Fe3+Sheet of adulterating fluorination bismuth anode material for lithium-ion batteries
Preparation method, it is characterised in that the fluorination bismuth prepared has more than 200mAh.g-1Specific capacity.
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| CN101212050A (en) * | 2007-12-21 | 2008-07-02 | 湘潭大学 | Method for producing bismuth trifluoride anode material of Li secondary battery |
| CN104150543A (en) * | 2014-07-14 | 2014-11-19 | 宁波大学 | Cu<2+>, Ce<4+>, Ag<+> doped iron fluoride composite positive pole material and preparation method thereof |
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| CN104150543A (en) * | 2014-07-14 | 2014-11-19 | 宁波大学 | Cu<2+>, Ce<4+>, Ag<+> doped iron fluoride composite positive pole material and preparation method thereof |
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