CN100517812C - Production method of lithium secondary battery drop water ferric fluoride anode material - Google Patents
Production method of lithium secondary battery drop water ferric fluoride anode material Download PDFInfo
- Publication number
- CN100517812C CN100517812C CNB2007101926816A CN200710192681A CN100517812C CN 100517812 C CN100517812 C CN 100517812C CN B2007101926816 A CNB2007101926816 A CN B2007101926816A CN 200710192681 A CN200710192681 A CN 200710192681A CN 100517812 C CN100517812 C CN 100517812C
- Authority
- CN
- China
- Prior art keywords
- fef
- mixture
- lithium secondary
- secondary battery
- alkali
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Images
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
Landscapes
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a preparation method for lithium secondary battery micro water ferric fluoride anode materials, wherein, firstly, teracidic malysite and alkali are uniformly mixed in an aqueous solution under normal temperature in proportion from 1 to 1 - 1 to 10; water is removed after sucking filtration; iron-alkali mixture is obtained after drying for 1 to 48 hours; secondly, the iron-alkali mixture and 5 to 40 percent hydrofluoric acids are uniformly reacted in a plastic sealed container in proportion from 1 to 1 - 1 to 10, and heat preservation is performed for 1 to 48 hours under the temperature of 40 to 100 DEG C; thirdly, mixture is filtered, cleaned by utilization of ethanol and dried for 1 to 36 hours in the air; fourthly, the mixture is dried for 1 to 72 hours under vacuum state of 50 to 250 DEG C; fifthly, the mixture is crushed in a ball mill and passes through a 100 to 400 mesh sieve, and then a ferric fluoride product is obtained. The invention has the advantages that: firstly, systematic temperature is automatically controlled, and technological parameters are determined through precise calculation on the basis; secondly, yield of the method is high and product purity is larger than 95 percent. Obtained FeF3 (H2O) 0.33 has an integrated orthorhombic system structure, regular surface topography, small grain diameter and uniform distribution, and good discharge performance. The method is a novel and practical technological line for preparation of the FeF3 (H2O) 0.33.
Description
Technical field
The present invention relates to a kind of preparation method of ferric flouride.
Background technology
Energy problem is the 21st century common problem human being face, and electric energy is a kind of energy form of most convenient, and for store electrical energy and the needs that satisfy the development of electronics industry develop rapidly and electric automobile, all kinds of batteries arise at the historic moment.Lithium secondary battery with excellent specific properties such as its high reversible capacity, high voltage, high cycle performance and high-energy-densities and enjoy common people to favor, is called as the leading power supply of 21 century, and its application constantly enlarges.But the lithium secondary battery industry competition is very fierce, seeks high-performance, the novel electrode material is the powerful measure that further reduces the battery cost, enhances the competitiveness cheaply.Therefore, the research of the novel positive and negative electrode material of lithium secondary battery is the key of lithium secondary battery development.The Arai of Kyoto Univ Japan etc. proposed with the positive electrode of transition metal fluorides as lithium secondary battery, with FeF in 1997
3Grind the back as anode with acetylene black, find FeF
3Discharge capacity between 4.5-2V is 80mAh/g, and theoretical capacity is 237mAh/g.The Briscoe of the U.S. etc. propose to use transition metal fluorides in the aerospace system power supply meeting of holding in April, 1999, as CuF
2Replace FeS
2Constitute Li/CuF
2Battery, its specific energy are 227Wh/kg, compare Li/FeS
2Battery is high by 40%; On U.S. MRS autumn sessions in 2002 and first international energy conversion engineering conference of holding in 2003, professor Amatucci has done " metal fluoride: nano-complex-positive electrode material of lithium secondary cell of new generation " report, and this seminar chemical reaction that began one's study from 2003 is stored the lithium secondary battery novel anode material of lithium, applied for that fluoride makes 2 United States Patent (USP)s of positive electrode, the Maier professor seminar of German Max Planck Institute for Solid State Research this class novel anode material that began one's study from 2003.For a positive active material, the key that obtain height ratio capacity is the various oxidation state that can make full use of material in oxidation-reduction process, and all electronics in the exchange material is similar to the reversible conversion reaction of formula (1), promptly following reaction:
NLi
++ ne+Me
N+X mouth nLiX+Me (1)
In general, the ionic bond intensity that increases Me-X will help to improve with the battery operated voltage of this material as electrode, and in the periodic table of elements, the electronegativity of fluorine is the strongest, the bond strength of the ionic bond compound that forms is more much higher than sulfide and nitride, the discharge potential platform is also much higher during therefore, as electrode material.Find but further analyze, although the discharge potential platform of transition metal fluorides than sulfide, nitrogenize object height, discharge capacity is low.In order further to improve the conductivity of fluoride, Amatucci seminar finds, with FeF
3With acetylene black or graphite by the high-energy ball milling of certain hour, make it become nanocarbon/metal fluoride nano composite material (CMFNCs), as FeF
3The nano-complex of/C=85/15wt%, the specific discharge capacity between 2.8-3.5V is up to 200mAh/g, near FeF
3Theoretical specific capacity 237mAh/g; And the discharge capacity based on reversible chemical reaction can reach 600mAh/g in the time of 70 ℃, is LiCoO
2Several times.The reason that its capacity is high is the chemical reaction of the CMFNCs of high conductivity based on formula (2) and (3), generates lithium fluoride and nano level metal Fe, and reaction is reversible.
Li
++e+FeF
3→LiFeF
3 (2)
2Li
++2e+LiFeF
3→3LiF+Fe (3)
System researches such as the Maier professor Li Hong of seminar lithium and metal fluoride constitute the reaction of battery, think that the electrochemical reversible of metal fluoride and lithium reacts can be expressed as formula (4):
M can be Ti in the formula, V, Mn, Fe, Co, Ni, Cu, Zn, Ag, Sn, n=2 or 3.According to the Nernst formula, find the anodal lithium secondary battery of aforementioned metal fluoride work by calculation of thermodynamics, its voltage is lower than the decomposition voltage 6.1V of pure LiF, than the about 1V of corresponding oxidation object height.Though domestic and international research work has obtained certain progress, its work reaches application level far away, even report best FeF at present
3/ C nano composite material, the life-span of its conductivity and battery awaits further to improve, capacity attenuation problem and cryogenic property problem await further investigation, and particularly how further improving electron conduction and ionic conductivity is to influence such material key in application.Prepare FeF at present both at home and abroad
3Main method be that anhydrous ferric chloride or iron oxide and dry hydrogen fluoride gas effect are generated amorphous FeF down
3,, need be heated to more than 1000 ℃ for obtaining crystallization; Perhaps at high temperature make F
2Be used for preparing with metallic iron or iron oxide.But this class reaction time consumption power consumption, and consumptive material height, the products obtained therefrom pattern depends on the original form of iron compound material powder.By our discovering, FeF
3(H
2O)
0.33Be to compare FeF
3The positive electrode material of lithium secondary cell of more excellent performance.
Summary of the invention
The purpose of this invention is to provide the method that a kind of solid-liquid legal system is equipped with ferric flouride.
The objective of the invention is to realize in the following way: a kind of lithium secondary battery FeF
3(H
2O)
0.33The preparation method of positive electrode:
(1) with trivalent iron salt and alkali in molar ratio 1: 1-1: 10 ratio mixes in the aqueous solution at normal temperatures, and suction filtration is removed water, dry 1-48 hour, iron alkali mixture;
(2) with the hydrofluoric acid of iron alkali mixture and 5-40% in molar ratio 1: 1-1: 10 ratio is homogeneous reaction in the plastic seal container, and 40-100 ℃ of insulation 1-48 hour;
(3) filter, with the ethanol cleaning and at air drying 1-36 hour;
(4) again under 50-250 ℃ of vacuum state dry 1-72 hour;
(5) in ball mill, pulverize, cross the 100-400 mesh sieve, get drop water ferric fluoride FeF
3(H
2O)
0.33Product.
Trivalent iron salt is FeNO
3, FeCl
3, Fe
2(SO
4)
3
Alkali is potassium hydroxide, NaOH, ammoniacal liquor.
The present invention has following beneficial effect, and the one, system temperature is controlled automatically, and determined technological parameter by accurate calculating on this basis; The 2nd, this method productive rate height, product purity is greater than 95%.The FeF that makes
3(H
2O)
0.33Have complete orthorhombic structure, surface topography rule, particle diameter is less and be evenly distributed, discharge performance is good, is preparation FeF
3(H
2O)
0.33A kind of novelty, practical process route.
Description of drawings
Fig. 1 is the FeF of preparation of the present invention
3(H
2O)
0.33The X-ray diffraction spectrogram;
Fig. 2 is the FeF of the present invention's preparation
3(H
2O)
0.33Stereoscan photograph;
Fig. 3 is the FeF of the present invention's preparation
3(H
2O)
0.33Be positive electrode, the lithium sheet is a negative material, is assembled into Li/FeF
3(H
2O)
0.33Button cell, the at room temperature discharge curve that discharges with the C/10 multiplying power;
Embodiment
The present invention will be further described below in conjunction with embodiment:
Embodiment 1:
Took by weighing FeCl in 1: 4 in molar ratio
3With the about 25g of ammoniacal liquor, make two kinds of materials mix suction filtration at normal temperatures in the aqueous solution, get iron alkali mixture,, put into special sealed plastic container the hydrofluoric acid of iron alkali mixture adding 40% in 1: 4 in molar ratio, be incubated 40 hours down at 50 ℃, it is mixed.The product that will react unnecessary is removed then, remaining material is cleaned with ethanol and in air atmosphere dry 24 hours, again with material 50 ℃ of vacuumizes 36 hours; Product is taken out, pulverize and in ball mill ball milling to 5～10 μ m, cross 300 mesh sieves, obtain purity greater than 95% FeF
3(H
2O)
0.33Product.
Embodiment 2:
Took by weighing Fe in 1: 8.5 in molar ratio
2(SO
4)
3With the about 25g of NaOH, two kinds of materials are mixed in the aqueous solution at normal temperatures, suction filtration is removed the water that generates, get iron alkali mixture, hydrofluoric acid with the adding 10% in 1: 7 in molar ratio of iron alkali mixture, put into special sealed plastic container, be incubated 30 hours down, it is mixed at 75 ℃.The product that will react unnecessary is removed then, remaining material is cleaned with ethanol and in air atmosphere dry 30 hours, again with material 90 ℃ of vacuumizes 64 hours; Product is taken out, pulverize and in ball mill ball milling to 5～10 μ m, cross 200 mesh sieves, obtain purity greater than 95% FeF
3(H
2O)
0.33Product.
Embodiment 3:
Took by weighing FeNO in 1: 6 in molar ratio
3With the about 25g of KOH, two kinds of materials are mixed in the aqueous solution at normal temperatures, suction filtration is removed the water that generates, get iron alkali mixture, with iron alkali mixture, the hydrofluoric acid of adding 30% in 1: 9 in molar ratio, put into special sealed plastic container, be incubated 36 hours down, it is mixed at 90 ℃.The product that will react unnecessary is removed then, remaining material is cleaned with ethanol and in air atmosphere dry 10 hours, again with material 190 ℃ of vacuumizes 24 hours; Product is taken out, pulverize and in ball mill ball milling to 5～10 μ m, cross 400 mesh sieves, obtain purity greater than 95% FeF
3(H
2O)
0.33Product.
Fig. 1 is the FeF of the present invention's preparation
3(H
2O)
0.33The X-ray diffraction spectrogram.As can be seen from the figure, the FeF that makes
3(H
2O)
0.33Have perfect orthorhombic structure, diffraction maximum is more sharp-pointed, does not almost have other impurity.
Fig. 2 is the FeF of the present invention's preparation
3(H
2O)
0.33Stereoscan photograph.As can be seen from the figure, the FeF that makes
3(H
2O)
0.33The surface topography rule, crystal grain is less and be evenly distributed, and is tiny and uniform structure helps the improvement of material electrochemical performance.
Fig. 3 is the FeF with the present invention's preparation
3(H
2O)
0.33Be positive electrode, the lithium sheet is a negative material, is assembled into Li/FeF
3(H
2O)
0.33Button cell, the at room temperature discharge curve that discharges with the C/10 multiplying power.As can be seen from the figure, relative cathode of lithium, FeF
3(H
2O)
0.33The discharge platform of 3.2～2.8V can be provided, and total specific discharge capacity reaches 190mAh/g.
Claims (3)
1, a kind of lithium secondary battery FeF
3(H
2O)
0.33The preparation method of positive electrode is characterized in that:
(1) with trivalent iron salt and alkali in molar ratio 1: 1-1: 10 ratio mixes in the aqueous solution at normal temperatures, and suction filtration is removed water, dry 1-48 hour, iron alkali mixture;
(2) with the hydrofluoric acid of iron alkali mixture and 5-40% in molar ratio 1: 1-1: 10 ratio is homogeneous reaction in the plastic seal container, and 40-100 ℃ of insulation 1-48 hour;
(3) filter, with the ethanol cleaning and at air drying 1-36 hour;
(4) again under 50-250 ℃ of vacuum state dry 1-72 hour;
(5) in ball mill, pulverize, cross the 100-400 mesh sieve, get FeF
3(H
2O)
0.33Product.
2, a kind of lithium secondary battery FeF according to claim 1
3(H
2O)
0.33The preparation method of positive electrode is characterized in that: trivalent iron salt is FeNO
3, FeCl
3, Fe
2(SO
4)
3
3, a kind of lithium secondary battery FeF according to claim 1
3(H
2O)
0.33The preparation method of positive electrode is characterized in that: alkali is potassium hydroxide, NaOH, ammoniacal liquor.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2007101926816A CN100517812C (en) | 2007-12-21 | 2007-12-21 | Production method of lithium secondary battery drop water ferric fluoride anode material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2007101926816A CN100517812C (en) | 2007-12-21 | 2007-12-21 | Production method of lithium secondary battery drop water ferric fluoride anode material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101222037A CN101222037A (en) | 2008-07-16 |
| CN100517812C true CN100517812C (en) | 2009-07-22 |
Family
ID=39631713
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2007101926816A Expired - Fee Related CN100517812C (en) | 2007-12-21 | 2007-12-21 | Production method of lithium secondary battery drop water ferric fluoride anode material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100517812C (en) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102315482B (en) * | 2011-08-31 | 2013-08-28 | 北京理工大学 | Lithium secondary battery with metal fluoride as positive electrode material |
| US9705124B2 (en) * | 2012-02-27 | 2017-07-11 | The Johns Hopkins University | High energy density Li-ion battery electrode materials and cells |
| CN102623707A (en) * | 2012-04-02 | 2012-08-01 | 湘潭大学 | Cobalt-doped carbon-coated ferric fluoride anode material and preparation method thereof |
| CN102826616B (en) * | 2012-09-13 | 2014-05-28 | 广东电网公司电力科学研究院 | Ferric fluoride nano material and preparation method thereof |
| CN103855389A (en) * | 2012-11-30 | 2014-06-11 | 海洋王照明科技股份有限公司 | Ferric (III) fluoride / carbon composite material and its preparation method and application |
| CN103151522B (en) * | 2013-02-28 | 2015-08-19 | 湘潭大学 | A kind of ferric fluoride anode material preparation method mixing crystal formation |
| CN103151523B (en) * | 2013-02-28 | 2015-07-22 | 湘潭大学 | Preparation method of cuboid-shaped positive-pole FeF3(H2O)0.33 material |
| CN103500830B (en) * | 2013-09-18 | 2016-07-06 | 宁波大学 | A kind of nitrogen doped silicon carbide assisted Solid-state one-step method ferric flouride lithium electricity positive electrode and preparation method |
| CN105336946B (en) * | 2015-09-28 | 2018-09-11 | 中国船舶重工集团公司第七一二研究所 | A kind of preparation method of lithium ion battery ferric fluoride anode material |
| CN106450179A (en) * | 2016-09-14 | 2017-02-22 | 湘潭大学 | Preparation method of titanium-doping ferric fluoride positive electrode material |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4938945A (en) * | 1988-10-18 | 1990-07-03 | Pennwalt Corporation | High purity anhydrous FeF3 and process for its manufacture |
-
2007
- 2007-12-21 CN CNB2007101926816A patent/CN100517812C/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4938945A (en) * | 1988-10-18 | 1990-07-03 | Pennwalt Corporation | High purity anhydrous FeF3 and process for its manufacture |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101222037A (en) | 2008-07-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100517812C (en) | Production method of lithium secondary battery drop water ferric fluoride anode material | |
| Pan et al. | Facile synthesis of M-Sb (M= Ni, Sn) alloy nanoparticles embedded in N-doped carbon nanosheets as high performance anode materials for lithium ion batteries | |
| CN101752555B (en) | Method for preparing lithium ion battery anode material LiFePO4 | |
| CN104900858B (en) | A kind of preparation method of sodium-ion battery yolk eggshell structure antimony/anode composite | |
| CN111793824B (en) | Surface-modified high-nickel cathode material and preparation method and application thereof | |
| Xie et al. | ZnO/Ni/C composite hollow microspheres as anode materials for lithium ion batteries | |
| CN102760876A (en) | Niobate and niobate composite material and application of niobate composite material to secondary lithium battery | |
| CN110148730A (en) | A kind of Gao Shouxiao long-life silicon based anode material and its preparation method and application | |
| CN102623705A (en) | Lithium ion battery cathode material LiFePO4/C, and preparation method and application thereof | |
| CN104445405A (en) | Preparation method of porous nanoscale TiNb2O7 | |
| CN106115785B (en) | A kind of pure phase MoO2Anode material of lithium-ion battery and preparation method thereof | |
| CN114242968A (en) | Carbon-coated sodium iron fluorophosphate material and preparation method and application thereof | |
| CN105826528B (en) | A kind of porous silicon-carbon/carbon-copper composite material and its preparation method and application | |
| CN109873150A (en) | The method for preparing nanometer silicon composite material as raw material using palygorskite | |
| CN106450179A (en) | Preparation method of titanium-doping ferric fluoride positive electrode material | |
| CN102437334B (en) | Microwave hydrothermal synthesizing method for carbon nanotube/LiFePO4 lithium ion battery anode material | |
| CN109802127A (en) | A kind of preparation method of Ag doping ferriferrous oxide nano composite material | |
| CN110364708B (en) | Preparation method of manganous manganic oxide-stannic oxide/cobaltosic oxide composite material | |
| Morimoto et al. | Charge/discharge behavior of triclinic LiTiOPO4 anode materials for lithium secondary batteries | |
| CN109888232A (en) | A kind of lithium ion battery porous nano silico-carbo composite negative pole material and preparation method thereof | |
| CN115072777B (en) | Method for preparing hollow bismuth sulfide through co-regulation of cobalt doping and solvent and potassium ion battery cathode material prepared by same | |
| CN109728290A (en) | A kind of preparation method and applications of transition metal oxide/graphitized intermediate-phase carbosphere composite material | |
| CN111211325B (en) | Lithium ion battery cathode material and preparation method and application thereof | |
| CN110176584B (en) | Preparation method of titanate composite negative electrode material for lithium ion battery | |
| Feng et al. | Effect of VO 4 3–Substitution on the Electrochemical Properties of a LiSn 2 (PO 4) 3 Anode Material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20090722 Termination date: 20131221 |