CN102623707A - Cobalt-doped carbon-coated ferric fluoride anode material and preparation method thereof - Google Patents
Cobalt-doped carbon-coated ferric fluoride anode material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a cobalt-doped carbon-coated ferric fluoride anode material and a preparation method thereof. The chemical formula of the ferric fluoride anode material of the cobalt coated carbon is Fe(1-x)CoxF3(H2O)0.33/C. The preparation method comprises the steps of adding iron source and cobalt source at the normal temperature into a hydrogen fluoride solution, and stirring the mixture to react in a sealed teflon reactor; continuously stirring the hydrogen fluoride solution to react after the temperature is raised, carrying out sucking and filtering, washing the obtained product with ethanol, drying the obtained product after washing, and carrying out heat treatment in vacuum to obtain cobalt-doped ferric fluoride powder; and pelletizing the cobalt-doped ferric fluoride powder and acetylene black, and carrying out heat treatment in vacuum to obtain the cobalt-doped carbon-coated ferric fluoride anode material. The preparation method disclosed by the invention has the following technical effects that (1) the prepared Fe(1-x)CoxF3(H2O)0.33/C has a complete orthorhombic system structure, the grain diameter of the ferric fluoride anode material of the cobalt coated carbon is small, and the ferric fluoride anode materials of the cobalt coated carbon are uniformly distributed; (2) the materials of Fe(1-x)CoxF3(H2O)0.33/C has favorable electrochemical cycling performance; and (3) the preparation method has the advantages of low required temperature and low cost, and is easy to industrially popularize.
Description
Technical field
The present invention discloses ferric fluoride anode material of mixing cobalt bag carbon and preparation method thereof, and this material can be used as anode material for lithium-ion batteries.
Background technology
The energy is the power of the national economic development, also is to weigh national overall national strength, and the important indicator of national civilized development degree and living standards of the people, development of human society be unable to do without the appearance of high-grade energy and the use of advanced energy technology.In the world today, the energy and environment are the whole world, whole mankind's questions of common interest, and chemical power source (battery) becomes desirable alternative energy source owing to easy to use, cheap, environmentally friendly.Follow the raising of development of high-tech and living standards of the people, the lithium ion battery manufacturing technology is showing improvement or progress day by day, and the battery cost reduces gradually, and therefore, lithium ion battery will become the main flow of chemical power source, and its application prospect is boundless.From the development of whole both positive and negative polarity electrode material, the key factor that restricts the lifting of lithium ion battery energy density at present is a positive electrode.Positive electrode is the important component part of lithium ion battery, accounts for about 46% of lithium ion battery cost, and its performance and price directly have influence on the performance and the price of lithium ion battery.Positive electrode also needs the irreversible capacity loss of added burden negative material.Therefore, the research of positive electrode is the key of lithium ion battery material research with improving always.
Using maximum positive electrodes at present mainly is laminar structure lithium cobalt oxide (LiCoO
2), lithium nickel oxide (LiNiO
2), spinel-type (LiMn
2O
4) and layer structure lithium manganese oxide (LiMnO
2), Dyadic transition metal oxide, ternary transition metal oxide, high voltage Li [M
0.5Mn
1.5] O
4With rich lithium type xLi
2MnO
3(1-x) LiMO
2Deng.
LiCoO
2Be typical case's representative of stratiform transition metal oxide positive electrode, its operating voltage is at 3.9V (vs.Li
+/ Li) about, have discharge steadily, be fit to advantages such as heavy-current discharge, specific energy height, good cycle, be to use the widest anode material for lithium-ion batteries.But at Li
xCoO
2In, x=0.5-1 promptly still has 0.5 Li in the charge and discharge process
+Electronics is not participated in electrode reaction, although its theoretical specific capacity is 274mAh/g, its actual capacity has only about 140mAh/g.Because cobalt resource is deficient, price is high, and when big electric current is used LiCoO
2Fail safe also be a major issue, thereby big limitations the scope of application of cobalt series lithium ion battery, especially aspect electric automobile and large-scale redundant electrical power.
The chemical property of nickel and cobalt is close basically, but price is more much lower than cobalt.LiNiO
2With LiCoO
2Have identical crystal structure, its theoretical reversible specific capacity is 275mAhg
-1, actual capacity reaches 170mAhg
-1More than.LiNiO
2Have high-temperature stability preferably, the low self-discharge rate has good compatibility with multiple electrolyte, and is free from environmental pollution, and resource is abundant relatively and price is suitable, but LiNiO
2Preparation technology too complicated, its application is restricted.Its main cause is the LiNiO of stoichiometric proportion under hot conditions
2Decompose excessive N i easily
2+Be in NiO
2In the lithium layer between the plane, hinder the diffusion of lithium ion, influenced the electro-chemical activity of material.Simultaneously because Ni
3+Compare Co
3+Seldom arrive LiNiO
2Synthetic need in oxygen atmosphere, carry out, condition is harsh.
Lithium manganese oxide is compared with cobalt with nickel, has cheap, resourceful advantage.The present LiMn2O4 that lithium manganate having spinel structure and layer structure are arranged of exploitation, they have other positive electrode incomparable physics and chemical property, its thermal safety and overcharging resisting electric energy power are fabulous, but LiMn
2O
4In use because the dissolvings of Mn etc. are prone to cause lattice to produce defective, make the crystal structure disordering, block the embedding of lithium ion and taken off the embedding passage, thereby caused the capacity attenuation of material very fast.Especially in the cycle performance sharp fall and the poor storage performance of high temperature (more than 45 ℃), limited its extensive use.
Olivine-type LiFePO
4Theoretical capacity be 170mAh/g, its thermal stability, fail safe and cycle life are good, but also have two defectives: 1. electronic conductivity is very little, is unfavorable for reversible reaction, particularly the carrying out of high-multiplying power discharge; 2. Li
+Diffusion in material is slower.In addition, synthetic desirable LiFePO
4And be not easy, when synthetic, also to prevent Fe
2+Be oxidized to Fe
3+
Li [Ni
0.5Mn
0.5] O
2Be typical case's representative of Dyadic transition metal oxide cathode material, had both the advantage of Mn system and Ni based material simultaneously, characteristic can be summarized as follows: (1) synthesis condition is comparatively gentle, and material cost is lower; (2) have higher specific discharge capacity, chargeable to 4.5V or higher current potential, obtain the capacity of about 180mAh/g, but cycle performance is desirable not enough.
Li [M
0.5Mn
1.5] O
4The theoretical capacity of high-voltage anode material is about 150mAh/g and have the high voltage platform of 4.7V, and energy density compares LiCoO
2Exceeding approximately 20%, be one type of very promising high voltage, high-energy-density spinel-type positive electrode, but its synthetic method awaits further further investigation.
Other anode material for lithium-ion batteries is like LiNi
1/3Mn
1/3Co
1/3O
2, vanadium the research work of materials such as compound of series compound, organic sulfur all carrying out among the active research both at home and abroad; Though obtained many useful achievements; The some of them material is used in industry, but other a part of material will be used await further perfect and in-depth in industry.
As the positive electrode of lithium secondary battery, metal fluoride is one type of promising anode material of lithium battery.Because the electronegativity of fluorine is big, the operating voltage of metal fluoride positive electrode is far above positive electrodes such as other metal oxides, metal sulfides.
Metal fluoride MeF
3Major part is PdF
3-ReO
3The type structure, PdF
3-ReO
3The MeF of type
3Has the structure that allows lithium ion to embed/deviate from.Metal fluoride and lithium metal not only can carry out lithium ion and embed/deviate from reaction, can also come storing energy suc as formula (1) with lithium generation reversible chemical conversion reaction.
The reversible chemical conversion reaction is the reversible redox reaction of positive electrode and lithium metal generation, and it is in the nature the chemical replacement reaction.This reversible chemical conversioning reaction can make full use of the various oxidation state of material in oxidation-reduction process, the lithium ion that all electronics in the exchange material, its capacity of emitting are higher than far away on traditional outline embeds/take off the embedding reaction.
But metal fluoride is out in the cold to a great extent, mainly is because of the strong ionic bond characteristic of metal fluoride, and big band gap has caused its poor electron conduction.Advantages such as the fluoride of iron is inexpensive, nontoxic with it, environmental protection and receiving much attention are study in the lithium secondary battery metal fluoride positive electrode maximum a kind of.The Fe-F compound has high-energy-density, high voltage, and charge-discharge performance is good, low cost, advantages such as high theoretical capacity, thereby be the positive electrode that has very much application prospect.In the last few years, external Amatucci seminar, Maier teaches seminar, and Tarascon seminar and the Fu Zhengwen of Fudan University professor seminar are all studied it.
Yet FeF
3Be a kind of broad-band gap insulator, this has seriously limited it in the coml practical application, in order to improve its electric conductivity, mainly is with FeF at present
3Thereby mix with electric conducting material and to improve its electric conductivity.Amatucci G.G etc. are through the nanometer Fe F of preparation carbon coated
3/ C composite material improves FeF
3Electric conductivity, yet its cycle performance still can not get improving, in order better to shorten FeF
3Band gap, improve its electric conductivity, can be through anion doped and cation doping FeF
3Realize.Because the radius and the Fe similar radius of metal Co, so the Co doping can improve FeF effectively
3Electric conductivity.Along with mixing of Co, FeF
3Band gap reduce, conductivity will strengthen, thus the electrochemistry cycle performance of material will significantly improve.FeF
3(H
2O)
0.33In contain a spot of crystallization water, the crystallization water has played the effect of stabilizing material structure in material, be considered to compare FeF
3Have better structural stability and chemical property.
Research work to this material has both at home and abroad obtained certain progress, but its work reaches application level far away.The best FeF of chemical property that reports at present
3(H
2O)
0.33Material is to utilize the low-temperature ion liquid phase method, selects for use 1-butyl-3 methyl imidazolium tetrafluoroborate (BmimBF4) ionic liquid as solvent and soft template, with Fe (NO
3)
39H
2The O reaction is gone up access FeF at SWCN (SWNT)
3Material, the SWNT/FeF that makes
3(H
2O)
0.33Composite material; But cycle performance is not fine; Circulating, its capability retention is merely 70% after 50 times, and the life-span of its conductivity and battery awaits further to improve, and particularly how further improving electron conduction and ionic conductivity is to influence the said material key in application.
Summary of the invention
Technical problem to be solved by this invention is: to FeF
3(H
2O)
0.33The problem of the electrochemistry cycle performance difference that exists provides a kind of ferric fluoride anode material of mixing cobalt bag carbon and preparation method thereof.
Technical scheme of the present invention is, a kind of ferric fluoride anode material of mixing cobalt bag carbon, and its chemical expression is: Fe
1-xCo
xF
3(H
2O)
0.33/ C, 0＜x in the formula≤0.1, the quality percentage composition 5%-20% of C in this material; Described C is an acetylene black.
A kind of preparation method who mixes the ferric fluoride anode material of cobalt bag carbon under the normal temperature, gets source of iron, cobalt source, adds hydrogen fluoride solution, stirring reaction in the polytetrafluoroethylene reactor of sealing; Intensification continued stirring reaction, suction filtration is used washing with alcohol, oven dry, heat treatment in a vacuum obtains mixing cobalt ferric flouride powder; Gained is mixed cobalt ferric flouride powder and acetylene black ball milling, obtain mixing the ferric fluoride anode material of cobalt bag carbon in a vacuum after the heat treatment.
The amount that adds source of iron and cobalt source is that 1～X: X confirms according to the atomic molar ratio of Fe and Co, wherein 0＜x≤0.1.
Said source of iron is Fe
2O
3, Fe (OH)
3In a kind of, the cobalt source is Co
2O
3, Co
3O
4, CoCO
3In a kind of, the concentration of hydrogen fluoride solution is 20～40wt%.
The time of said stirring reaction at normal temperatures is 2～6 hours, and the temperature after the intensification is 70～80 ℃, and the time of the stirring reaction after the intensification is 12～36 hours.
After the said washing with alcohol, the temperature of oven dry is 60～80 ℃.
The time of said ball milling is 1～6 hour, and the heat treatment time behind the ball milling is 2～6 hours, and temperature is 150～180 ℃.
The present invention has following technique effect, the Fe of (1) preparation
1-xCo
xF
3(H
2O)
0.33/ C has complete orthorhombic structure, and particle diameter is less and be evenly distributed; (2) Fe
1-xCo
xF
3(H
2O)
0.33/The C material has excellent electrochemistry cycle performance; (3) this preparation method is temperature required low, with low cost, is easy to industry and promotes.
Description of drawings
Fig. 1 is the Fe of the present invention's preparation
0.95Co
0.05F
3(H
2O)
0.33The stereoscan photograph of/C.
Fig. 2 is the Fe of the present invention's preparation
0.95Co
0.05F
3(H
2O)
0.33The X-ray diffraction spectrogram of/C.
Fig. 3 is the Fe of the present invention's preparation
0.95Co
0.05F
3(H
2O)
0.33/ C is as positive electrode, and the lithium sheet is a negative material, is assembled into button cell, the first charge-discharge curve that at room temperature discharges and recharges with 0.1C and 1.0C multiplying power.
Fig. 4 is the Fe with the present invention's preparation
0.95Co
0.05F
3(H
2O)
0.33/ C is a positive electrode, and the lithium sheet is a negative material, is assembled into button cell, at room temperature with the cycle life curve under 0.1C and the 1.0C multiplying power.
Embodiment
Below in conjunction with specific embodiment the present invention is further specified
Embodiment 1:
Mol ratio by n (Fe): n (Co)=0.95: 0.05 takes by weighing Fe
2O
3And Co
2O
3About 10g, after mixing, normal temperature and constantly stirring down added the HF of 40wt% in 1: 4 in molar ratio, put into the polytetrafluoroethylcontainer container of sealing, and 25 ℃ are stirred 4h down.Be warming up to then 75 ℃ fully reaction until generating pink solid, with the gained material with washing with alcohol 3 times and in air atmosphere 60 ℃ of dry 10h, again with material at 160 ℃ of following vacuumize 5h.Obtain purity greater than 96% Fe
0.95Co
0.05F
3(H
2O)
0.33Product, with its mix with 15wt% acetylene black, ball milling 3h, 150 ℃ of vacuum heat-preserving 6h cross 400 mesh sieves, obtain Fe
0.95Co
0.05F
3(H
2O)
0.33/ C composite material.
Embodiment 2:
Mol ratio by n (Fe): n (Co)=0.97: 0.03 takes by weighing Fe
2O
3And Co
3O
4About 10g, after mixing, normal temperature and constantly stirring down added the HF of 30wt%% in 1: 6 in molar ratio, put into the polytetrafluoroethylcontainer container of sealing, and 30 ℃ are stirred 3h down.Be warming up to then 80 ℃ fully reaction until generating the grey black solid, with the gained material with washing with alcohol 3 times and in air atmosphere 80 ℃ of dry 6h, again with material at 170 ℃ of following vacuumize 4h.Obtain purity greater than 96% Fe
0.97Co
0.03F
3(H
2O)
0.33Product, with its mix with 20wt% acetylene black, ball milling 3h, 160 ℃ of vacuum heat-preserving 5h cross 400 mesh sieves, obtain Fe
0.97Co
0.03F
3(H
2O)
0.33/ C composite material.
Embodiment 3:
Mol ratio by n (Fe): n (Co)=0.92: 0.08 takes by weighing industrial Fe (OH)
3And CoCO
3About 10g added the HF of 20wt% in 1: 8 in molar ratio, put into the polytetrafluoroethylcontainer container of sealing, and 25 ℃ are stirred 6h down, it is mixed.Be warming up to then 75 ℃ fully reaction until generating pink solid, with the gained material with washing with alcohol 3 times and in air atmosphere 80 ℃ of dry 6h, again with material at 180 ℃ of vacuumize 2h.Product is taken out, pulverize, cross 400 mesh sieves, obtain purity greater than 96% Fe
0.92Co
0.08F
3(H
2O)
0.33Product.With itself and 15wt% acetylene black ball milling 3h, 180 ℃ of vacuum heat-preserving 2h, cross 400 mesh sieves, obtain Fe
0.92Co
0.08F
3(H
2O)
0.33/ C composite material.
As shown in Figure 1, as can be seen from the figure, the Fe that makes
0.95Co
0.05F
3(H
2O)
0.33/ C surface topography rule, crystal grain is less and be evenly distributed, and this tiny and uniform structure helps the embedding of Li+ and deviates from, thereby helps improving the chemical property of material.
As shown in Figure 2, as can be seen from the figure, the Fe that makes
0.95Co
0.05F
3(H
2O)
0.33/ C has perfect orthorhombic structure, and diffraction maximum is more sharp-pointed, does not almost have other impurity.
As shown in Figure 3, with the Fe of the present invention's preparation
0.95Co
0.05F
3(H
2O)
0.33/ C is as positive electrode, and the lithium sheet is a negative material, is assembled into button cell, the first charge-discharge curve that at room temperature discharges and recharges with 0.1C and 1.0C multiplying power.Can find out relative cathode of lithium, Fe in from figure
0.95Co
0.05F
3(H
2O)
0.33/ C can provide the discharge platform of 3.2～2.8V, and first discharge specific capacity approaches theoretical capacity (237mAh/g) up to 223.7mAh/g.
As shown in Figure 4, with the Fe of the present invention's preparation
0.95Co
0.05F
3(H
2O)
0.33/ C is a positive electrode, and the lithium sheet is a negative material, is assembled into button cell, at room temperature with the cycle life curve under 0.1C and the 1.0C multiplying power.As can be seen from the figure, Fe
0.95Co
0.05F
3(H
2O)
0.33/ C makees the battery that positive electrode assembles and discharges and recharges, and its capability retention that circulates after 100 times is up to 91%.
Claims (7)
1. ferric fluoride anode material of mixing cobalt bag carbon, its chemical expression is: Fe
1-xCo
xF
3(H
2O)
0.33/ C, 0＜X in the formula≤0.1, the quality percentage composition 5%-20% of C in this material; C is an acetylene black.
2. a preparation method who mixes the ferric fluoride anode material of cobalt bag carbon is characterized in that: under the normal temperature, get source of iron, cobalt source, add hydrogen fluoride solution, stirring reaction in the polytetrafluoroethylene reactor of sealing; Intensification continued stirring reaction, suction filtration is used washing with alcohol, oven dry, heat treatment in a vacuum obtains mixing cobalt ferric flouride powder; Gained is mixed cobalt ferric flouride powder and acetylene black ball milling, obtain mixing the ferric fluoride anode material of cobalt bag carbon in a vacuum after the heat treatment.
3. the preparation method who mixes the ferric fluoride anode material of cobalt bag carbon according to claim 2 is characterized in that: the amount that adds source of iron and cobalt source is that 1～X: X confirms according to the atomic molar ratio of Fe and Co, wherein 0＜X≤0.1.
4. the preparation method who mixes the ferric fluoride anode material of cobalt bag carbon according to claim 2 is characterized in that: said source of iron is Fe
2O
3, Fe (OH)
3In a kind of, the cobalt source is Co
2O
3, Co
3O
4, CoCO
3In a kind of, the concentration of hydrogen fluoride solution is 20～40wt%.
5. the preparation method who mixes the ferric fluoride anode material of cobalt bag carbon according to claim 2; It is characterized in that: the time of said stirring reaction at normal temperatures is 2～6 hours; Temperature after the intensification is 70～80 ℃, and the time of the stirring reaction after the intensification is 12～36 hours.
6. the preparation method who mixes the ferric fluoride anode material of cobalt bag carbon according to claim 1 is characterized in that: after the said washing with alcohol, the temperature of oven dry is 60～80 ℃.
7. the preparation method who mixes the ferric fluoride anode material of cobalt bag carbon according to claim 1, it is characterized in that: the time of said ball milling is 1～6 hour, and the heat treatment time behind the ball milling is 2～6 hours, and temperature is 150～180 ℃.
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