CN103435105A - Iron oxide/carbon composite lithium ion battery anode material as well as preparation method and application thereof - Google Patents
Iron oxide/carbon composite lithium ion battery anode material as well as preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to a preparation method for iron oxide/carbon composite material. The preparation method comprises the steps as follows: 1, taking a water-soluble iron salt as an iron source, taking a water-soluble organic carbon source as a carbon source, and uniformly mixing the iron salt water solution, ammonia water with the organic carbon source to form a liquid phase mixture; 2, performing spray drying, freeze drying or spray pyrolysis on the liquid phase mixture to form a powder precursor, and performing calcination on the precursor to prepare into the iron oxide/carbon composite material; or performing spray pyrolysis on the mixed solution directly to prepare into the iron oxide/carbon composite material. The preparation method for the iron oxide/carbon composite material, which is provided by the invention, is high in production efficiency and suitable for large-scale production; the utilization efficiency of the composite material is improved; the iron oxide/carbon composite material provided by the invention is taken as the anode material of a lithium ion battery, so that the lithium storage capacity of the anode material of the lithium ion battery is several times as much as that of commercial carbon anode material.
Description
Technical field
The invention belongs to field of energy source materials.Be specifically related to a kind of Novel cathode material for lithium ion battery and preparation method thereof, use negative pole and the lithium ion battery thereof of this material.
Technical background
Along with modern society to energy demand day by day increase and to the raising day by day of environmental protection requirement; the contradiction of the continuous exhaustion of tradition petrochemical industry resource and the development of its pollution to environment and modern society is increasingly sharpened; lithium ion battery is as the green secondary power supply grown up over a kind of nearly 20 years; because its energy density is high, have extended cycle life, self-discharge is little, memory-less effect, advantages of environment protection, in the power supply of the small portable movable electrical appliances such as computer, mobile telephone, MP3, be used widely.The at present deposit of electromobile, hybrid-electric car, electric bicycle, sun power and wind energy and conversion, power tool increase day by day to the demand of the secondary power supply of the high-energy-density of safety, environmental protection and high power density, and wherein lithium ion battery has the potentiality that meet its application requiring.The lithium ion battery negative material of current unique large-scale commercial is mainly the graphite carbon material, but its theoretical capacity is about 372 mAh/g, can not meet the requirement of high power density, high-energy-density.Graphite carbon not only theoretical capacity is low, and its weight density only has 2.2～2.4 g/cm
3, this has reduced the volume capacity of battery to a great extent, particularly unfavorable to the volume density of large-sized battery.Thereby many countries have all dropped into a large amount of energy and financial resources the negative material of lithium ion battery are conducted extensive research and develops in recent years.
The oxide compound of the transition metal such as Ti, Fe, Cu, Co and Ni has the characteristic of heavy body as lithium ion battery negative material, have the possibility of potential alternative graphite carbon negative material.Following reaction occurs in transition metal oxide in electrochemistry removal lithium embedded process as lithium ion battery negative material:
In formula, M is transition metal oxide.Transition metal oxide has larger volumetric expansion in embedding lithium process, makes material generation efflorescence, loses effectively and electrically contacts, and the cyclical stability of material is poor.In addition, due to the Li generated in embedding lithium process first
2the O part is irreversible and due to the formed irreversible capacity of solid electrolyte film (SEI film) formed in the ubiquitous electrode materials in negative material surface and electrolytic solution reaction, makes also ubiquity irreversible high shortcoming first of transition metal oxide.In the transition metal oxide negative material, ferriferous oxide is because its capacity is high, cheap, wide material sources, safety non-toxic and the easy advantage such as storage and receiving much attention.As Fe
2o
3and Fe
3o
4theoretical capacity as lithium ion battery negative material reaches respectively 1005 mAh/g and 926 mAh/g, is about 3 times of graphite cathode material.In addition, the weight density of ferriferous oxide is about 5.2 g/cm
3, be approximately 2.5 times of graphite, thereby ferriferous oxide have higher volume and capacity ratio as lithium ion battery negative material, this has obvious advantage for its commercialization practical application.Indulge the above, the ferriferous oxide negative material is a kind of lithium ion battery negative material of new generation that has development and application potential.But also needing the subject matter solved is when keeping the material high capacity characteristics, improves the cycle performance of material and reduce the irreversible capacity first of material.
Summary of the invention
In order to solve the problems of the technologies described above, first purpose of the present invention is to provide a kind of preparation method of ferriferous oxide/carbon composition lithium ion battery cathode material.Ferriferous oxide/carbon once forms simultaneously, and the method technique is simple, and the starting material source is abundant, with low cost, is applicable to large-scale production.Second purpose of the present invention is to provide ferriferous oxide/carbon compound cathode materials prepared by aforesaid method.In this material, ferriferous oxide mainly is embedded in carbon base body, and both contact closely.Ferriferous oxide has kept the characteristic of its heavy body, the introducing of carbon has not only effectively improved the electronic conductivity between iron oxide particle, also effectively cushion the volume change of ferriferous oxide in the removal lithium embedded process, reduced the efflorescence of iron oxide particle, effectively improved the utilization ratio of material.This ferriferous oxide/carbon composite has advantages of that charge/discharge capacity is high, good cycle.The 3rd purpose of the present invention is to provide the lithium ion battery negative that uses this matrix material.The 4th purpose of the present invention is to provide the lithium ion battery that uses this negative pole.
In order to realize first above-mentioned purpose, the present invention has adopted following technical scheme:
A kind of preparation method of ferriferous oxide/carbon composite, the method comprises the following steps:
1) take water-soluble molysite as source of iron,
take the Water Soluble Organic Carbon source as carbon source, molysite aqueous solution and ammoniacal liquor and organic carbon source are mixed, obtain liquid phase mixture;
2) to this liquid phase mixture, adopt the method for spraying drying, lyophilize or spraying cracking to form the powder presoma, then this presoma is calcined, be prepared into ferriferous oxide/carbon composite; Perhaps, directly to the cracking of being sprayed of this mixing solutions, be prepared into ferriferous oxide/carbon composite; 5～70 wt% that in described ferriferous oxide/carbon composite, the content of carbon is the matrix material mass percent, preferably the content of carbon is 20～60% of matrix material mass percent, the amorphous compound that described ferriferous oxide is iron and oxygen, FeO, Fe
3o
4, Fe
2o
3in one or more.
As preferably, described water-soluble molysite is one or more mixing in iron trichloride, iron protochloride, ironic oxalate, iron nitrate, ferric sulfate and ferrous sulfate and their crystalline hydrate, is preferably lower-cost iron trichloride or its crystalline hydrate.
As preferably, described
the Water Soluble Organic Carbon sourcefor one or more in citric acid, lauric acid, sucrose, glucose and polyvinyl alcohol.
As preferably, the mol ratio of described water-soluble molysite and ammoniacal liquor is 1:(0.2 ~ 20), be preferably 1:(1 ~ 5); Molysite with
water-solublethe mol ratio of organic carbon source is 1:(0.2 ~ 8), be preferably 1:(0.5 ~ 5); The saturated volumetric molar concentration that the volumetric molar concentration of water-soluble molysite is 0.5 mol/L～molysite, the concentration of ammoniacal liquor is 3～15 mol/L.
As preferably, described liquid phase mixture adopts spraying drying to prepare the powder presoma, and drying temperature is 100～500 ℃, preferably 150～400 ℃; Dry atmosphere can adopt the mixed gas of air, nitrogen, argon gas or above one or more gases, is preferably air; Then, the powder presoma that drying is obtained is calcined, and calcining temperature is 300～900 ℃, is preferably 350～700 ℃; Calcination atmosphere can adopt the mixed gas of air, nitrogen, argon gas, hydrogen, methane, ammonia or above one or more gases; The time of calcining is 0.5 ~ 6 hour, is preferably 1 ~ 4 hour.
As preferably, described liquid phase mixture is under the mixed gas of air, nitrogen, argon gas or above one or more gases, and the cracking of spraying under 300～900 ℃, directly form ferriferous oxide/carbon composite; As preferably, the spraying cracking temperature is 350～800 ℃, and cracking atmosphere adopts air.
As preferably, described liquid phase mixture is sprayed and is cracked into the powder presoma under 100～500 ℃ at the mixed gas of air, nitrogen, argon gas or above one or more gases, and then under 300～900 ℃, calcine in inert atmosphere 0.5～6 hour, form ferriferous oxide/carbon composite; The mixed gas that inert atmosphere is nitrogen, argon gas or nitrogen and argon gas; As preferably, cracking atmosphere adopts air; As preferably, calcination atmosphere adopts nitrogen, and calcination time is 1 ~ 4 hour.
As preferably, described liquid phase mixture adopts lyophilize to prepare the powder presoma,, drying temperature be-10～-70 ℃, is preferably-20～-50 ℃, and the employing dynamic vacuum; Then, the powder presoma that drying is obtained is calcined, and calcining temperature is 300～900 ℃, is preferably 350～700 ℃; Calcination atmosphere can adopt the mixed gas of air, nitrogen, argon gas, hydrogen, methane, ammonia or above one or more gases; The time of calcining is 0.5 ~ 6 hour, is preferably 1 ~ 4 hour.
In order to realize second above-mentioned purpose, the present invention has adopted following technical scheme:
Ferriferous oxide/carbon composition lithium ion battery cathode material, this material adopts the above described method of any one technical scheme to prepare.
In order to realize the 3rd above-mentioned purpose, the present invention has adopted following technical scheme:
Lithium ion battery negative, adopt described negative material and binding agent, conductive agent to be mixed to form slurry in solvent, and slurry is coated to Copper Foil, foam copper or nickel foam collection liquid surface, after oven dry and compacting, obtains lithium ion battery negative.
As preferably, the process of making lithium ion battery negative is as follows: by described ferriferous oxide/carbon compound cathode materials, conductive agent and binding agent by 8:(0～2): the mass ratio of (0.5～2) joins in solvent and mixes, be coated on collector, then dry, make lithium ion battery negative.
In lithium ion battery negative of the present invention, described binding agent can be used conventional binding agent well known by persons skilled in the art, as polyvinylidene difluoride (PVDF) (PVDF), polytetrafluoroethylene (PTFE), styrene-butadiene rubber(SBR) (SBR) and Xylo-Mucine (CMC).
In lithium ion battery negative of the present invention, described collector can be used conventional collector well known by persons skilled in the art, as Copper Foil, foam copper, nickel foam.
In lithium ion battery negative of the present invention, conductive agent can adopt one or more in those skilled in the art's acetylene black commonly used, carbon black, Ketjen black, graphite, carbon fiber.
In lithium ion battery negative of the present invention, solvent can adopt those skilled in the art N-methyl-pyrrolidone (NMP) or water commonly used.
In order to realize the 4th above-mentioned purpose, the present invention has adopted following technical scheme:
Lithium ion battery, this lithium ion battery adopts the anodal and in-between barrier film of described negative pole, removal lithium embedded and the lithium ion battery that electrolytic solution forms.
The positive electrode material of removal lithium embedded ion can adopt various conventional positive electrode active materials well known by persons skilled in the art, as LiCoO
2, LiFePO
4, LiMnPO
4, LiMnO
2, LiMn
2o
4, LiVPO
4f, LiNiO
2.
In lithium ion battery of the present invention, ionogen can be conventional nonaqueous electrolytic solution well known by persons skilled in the art, and wherein in electrolytic solution, lithium salts can be lithium hexafluoro phosphate (LiPF
6), lithium perchlorate (LiClO
4), LiBF4 (LiBF
4), hexafluoroarsenate lithium (LiAsF
6), fluorocarbon based Sulfonic Lithium (LiC (SO
2cF
3)
3) in one or more.Non-aqueous solvent can be chain acid fat and ring-type acid fat mixing solutions, and wherein chain acid fat can be one or more in dimethyl carbonate (DMC), diethyl carbonate (DEC), methyl ethyl carbonate fat (EMC); Ring-type acid fat can be one or more in ethylene carbonate (EC), propene carbonate (PC), the inferior ethene fat of carbonic acid (VC).The concentration of electrolyte lithium salt is generally 0.7 ~ 1.3 mol/L.
After adopting technique scheme, beneficial effect of the present invention is as follows:
1. the outstanding advantage of the present invention is to the invention provides a kind of method for preparing ferriferous oxide/carbon composite, and the method is simple, and production efficiency is high, is applicable to large-scale production, the cheap and wide material sources of the prices of raw and semifnished materials;
2. another advantage of the present invention is that iron oxide particle mainly is embedded in carbon or by carbon and coats due to carbon and once formation simultaneously of ferriferous oxide, and contacting of carbon and ferriferous oxide is tight.The introducing of carbon has not only improved the electronic conductivity of matrix material greatly, also effectively suppress the volumetric expansion of ferriferous oxide in the doff lithium process, reduce efflorescence, can greatly improve the utilising efficiency of matrix material, and ferriferous oxide has kept the characteristic of its heavy body in matrix material.Of the present invention to also have an advantage be the amorphous compound that the ferriferous oxide that obtains is iron and oxygen, Fe
3o
4, Fe
2o
3or hold concurrently containing above two-phase or three-phase;
3. ferriferous oxide/carbon composite provided by the invention, as lithium ion battery negative material, has the lithium storage content that is several times as much as the business carbon negative pole material.Ferriferous oxide/carbon composite provided by the invention is as lithium ion battery negative material, its first loading capacity can reach 1380 mA h/g, reversible capacity can reach 960 mA h/g first, the specific storage of material is high, and stable circulation is good;
4. the density of ferriferous oxide is about 5 g/cm
3, be density (2.2～2.4 g/cm of carbon material
3) more than 2 times.Therefore, with ferriferous oxide/carbon compound cathode materials of the present invention, there is the tap density higher with carbon negative pole material than current business, for lithium ion battery negative material, there is higher volume and capacity ratio.
The accompanying drawing explanation
Fig. 1 is the X-ray diffracting spectrum of ferriferous oxide/carbon composite of obtaining of embodiment 1.
Fig. 2 is the scanning electron microscope pattern of ferriferous oxide/carbon composite of obtaining of embodiment 1.Insertion figure in figure is the selected diffraction figure of non-crystal oxide under transmission electron microscope existed in matrix material.
Fig. 3 is the cycle performance figure of ferriferous oxide/carbon compound cathode materials of obtaining of embodiment 1.
Fig. 4 is the cycle performance figure of ferriferous oxide/carbon compound cathode materials of obtaining of embodiment 2.
Fig. 5 is the cycle performance figure of ferriferous oxide/carbon compound cathode materials of obtaining of embodiment 3.
Fig. 6 is the x-ray diffraction pattern of ferriferous oxide/carbon composite of obtaining of embodiment 4.
Fig. 7 is the scanning electron microscope pattern of ferriferous oxide/carbon composite of obtaining of embodiment 4.
Fig. 8 is the cycle performance figure of ferriferous oxide/carbon compound cathode materials of obtaining of embodiment 4.
Fig. 9 is the cycle performance figure of ferriferous oxide/carbon compound cathode materials of obtaining of embodiment 5.
Figure 10 is the cycle performance figure of ferriferous oxide/carbon compound cathode materials of obtaining of embodiment 6.
Figure 11 is the cycle performance figure of ferriferous oxide/carbon compound cathode materials of obtaining of embodiment 7.
Figure 12 is the scanning electron microscope pattern of ferriferous oxide/carbon composite of obtaining of embodiment 8.
Figure 13 is the x-ray diffraction pattern of ferriferous oxide/carbon composite of obtaining of embodiment 8.
Figure 14 is the x-ray photoelectron spectroscopy of ferriferous oxide/carbon composite of obtaining of embodiment 8.
Figure 15 is the transmission electron microscope pattern of ferriferous oxide/carbon composite of obtaining of embodiment 8.Insertion figure in figure is the selected diffraction figure of non-crystal oxide under transmission electron microscope existed in matrix material.
Figure 16 is the cycle performance figure of ferriferous oxide/carbon compound cathode materials of obtaining of embodiment 8.
Embodiment
The present invention may be better understood for following examples, but the present invention is not limited to following examples.In addition, after having read content of the present invention, those skilled in the art can make various changes or modifications the present invention, and these equivalent form of values fall within the application's appended claims limited range equally.
embodiment 1
Adopt FeCl
3as source of iron, be made into the solution that volumetric molar concentration is 2.2 mol/L.This solution is heated to 100 ℃, will with FeCl
3the ammoniacal liquor of the ratio that mol ratio is 10:1 (15 mol/L) joins FeCl
3in the aqueous solution, and add and FeCl
3the citric acid that mol ratio is 3:1, go into liquid form mixt after fully stirring.Above-mentioned solution is sprayed in 400 ℃ of air cracking, obtain the powder presoma.Again by this powder presoma under nitrogen atmosphere, within 3 hours, obtain ferriferous oxide/carbon composite through 450 ℃ of calcinings.Through X-ray diffraction, detect, in matrix material, crystalline oxide is mainly Fe
3o
4.Through the elemental microanalysis method analysis, in matrix material, carbon content is 20% of matrix material weight percent.Choose diffraction analysis through transmission electron microscope, also contain amorphous ferriferous oxide in matrix material.
The preparation of negative pole: the N-methyl-pyrrolidone (NMP) of take is solvent, quality proportioning by above-mentioned iron-based oxide/carbon matrix material and conductive agent acetylene black and binding agent polyvinylidene difluoride (PVDF) (PVDF) by 8:1:1 mixes, be coated on the collector nickel foam, then 120 ℃ of oven dry, rolling formation after dry, cut-parts make the negative pole of desired size.
The preparation of lithium ion battery:
The iron lithium phosphate that is 8:1:1 by weight ratio, conductive agent acetylene black, poly(vinylidene fluoride) (PVDF) join in N-methyl-pyrrolidone (NMP) solvent, after stirring, make anode sizing agent; Anode sizing agent is coated on aluminium foil equably, rolling formation after drying, cut-parts make the lithium ion cell positive of 53 millimeters (length) * 30 millimeter (wide).
Include in after the lithium ion cell positive that makes, barrier film, negative pole lamination successively is good in the square aluminum hull of 55 millimeters * 34 millimeters * 6 millimeters, will contain the lithium hexafluoro phosphate (LiPF of 1 mol/L
6) ethylene carbonate: methylcarbonate (EC/DMC) is by volume for 1:1:1 is made into electrolytic solution, injects electrolytic bath, and the sealed cell aluminum hull can make lithium ion battery.
Ferriferous oxide/carbon composite capacity and cycle performance test: capacity and the cycle performance of the ferriferous oxide/carbon compound cathode materials that adopts simulated battery to prepare the present embodiment are tested.N-methyl-the pyrrolidone (NMP) of take is solvent, quality proportioning by preparation-obtained ferriferous oxide/carbon composite, acetylene black and binding agent polyvinylidene difluoride (PVDF) (PVDF) by 8:1:1 mixes, be coated on the collector nickel foam, then suppress after 120 ℃ of oven dry, make test electrode.The metallic lithium of take is test electrode to electrode, adopts 2025 type button cells to be tested.Put into 2025 button cell shells after test electrode, barrier film (Celgard 2400), lithium tinsel lamination successively is good, with the lithium hexafluoro phosphate (LiPF of 1 mol/L
6) ethylene carbonate: methylcarbonate (EC/DMC, volume ratio is 1:1) solution is as electrolytic solution, at H
2o and O
2content all is less than in the glove box of 0.1 ppm, adopts sealing machine sealed cell shell to make lithium ion battery.Adopt Neware battery test system (specification 5 V, 2 mA) to carry out the constant current charge-discharge test to assembled simulated battery.Test current is 100 mA/g, and voltage range is 0～3 V.
The x-ray diffraction pattern of ferriferous oxide/carbon composite that Fig. 1 is the present embodiment acquisition.Visible, the crystalline oxide in matrix material is mainly Fe
3o
4, other is also containing a small amount of Fe
8+3(O, OH)
16cl
1.3by product.
The scanning electron microscope pattern of ferriferous oxide/carbon composite that Fig. 2 is the present embodiment acquisition, the irregular particle that matrix material mainly is comprised of ferriferous oxide and carbon forms, and particle size is micron order.Insertion figure in figure be in this matrix material under transmission electron microscope the selected diffraction figure in energy spectrum analysis iron content and oxygen zone, the existence of amorphous oxides has been described.
The cyclic curve figure of ferriferous oxide/carbon composite that Fig. 3 is the present embodiment acquisition, this material has heavy body and good cyclical stability concurrently as lithium ion battery negative material as seen.The electric discharge first of this ferriferous oxide/carbon material can reach 1370 mAh/g, and reversible capacity is 960 mAh/g first, and the capacity after 200 circulations is 850 mAh/g, capability retention nearly 90%.The matrix material capacity only slightly descends in initial several working cyclees, subsequently until in the process of 200 circulations capacity almost do not descend.
embodiment 2
Adopt FeCl
3as source of iron, be made into the solution that volumetric molar concentration is 4.0 mol/L.At room temperature, in this solution, add and FeCl
3the mol ratio ammoniacal liquor (concentration is 8 mol/L) that is 8:1, and then add and FeCl
3the mol ratio citric acid that is 3:1, stir, form liquid phase mixture.By above-mentioned liquid phase mixture, in the air atmosphere of 400 ℃, the cracking of being sprayed, form powder body material.Again to this powder body material at N
2under atmosphere, through 500 ℃ of calcinings, within 3 hours, obtain ferriferous oxide/carbon composite.Through X-ray diffraction, detect, in matrix material, crystalline oxide is mainly Fe
3o
4.Selected diffraction analysis through transmission electron microscope energy spectrum analysis iron content and oxygen zone, contain amorphous oxides in material.Through the elemental microanalysis method analysis, in matrix material, carbon content is 15% of matrix material weight percent.
Adopt the method identical with embodiment 1 to be tested the chemical property of this matrix material, the loading capacity first of material reaches 1380 mAh/g, reversible capacity reaches 960 mAh/g first, and the capacity after 200 circulations is 780 mAh/g, and capability retention is 76%.Fig. 4 is that the present embodiment obtains the cycle performance of matrix material as lithium ion battery negative material.
Adopt the method identical with embodiment 1 to take this matrix material and be prepared into negative pole and lithium ion battery as negative material.
Adopt FeCl
3as source of iron, be made into the solution that volumetric molar concentration is 2.2 mol/L.This solution is heated to 50 ℃, adds and FeCl in solution
3mol ratio be 12:1 ammoniacal liquor (1.5 mol/L) stirs, and then add and FeCl
3the mol ratio citric acid that is 4:1, stir, form liquid phase mixture.By above-mentioned liquid phase mixture, in the air atmosphere of 300 ℃, the cracking of being sprayed, form powder body material.Again to this powder body material at N
2under atmosphere, through 450 ℃ of calcinings, within 3 hours, obtain ferriferous oxide/carbon composite.Through X-ray diffraction, detect, in matrix material, crystalline oxide is mainly Fe
3o
4.Through the elemental microanalysis method analysis, in matrix material, carbon content is 25% of matrix material weight percent.
Adopt the identical method of embodiment 1 to be assembled into simulated battery, test the chemical property of this matrix material.The loading capacity first of this material is 1360 mAh/g, and reversible capacity is 940 mAh/g first, and the capacity after 200 circulations is 800 mAh/g, and capability retention is 85%.The cycle performance curve that Fig. 5 is the matrix material that obtains of the present embodiment, visible material only in initial several circulations capacity slightly descend, subsequently until in 200 circulations capacity substantially remain unchanged.
The preparation of negative pole: the N-methyl-pyrrolidone (NMP) of take is solvent, by above-mentioned iron-based oxide/carbon matrix material: the conductive agent Ketjen black: binding agent polyvinylidene difluoride (PVDF) (PVDF) mixes by the quality proportioning of 8:0.5:1, be coated on the collector nickel foam, then 120 ℃ of oven dry, rolling formation after drying, cut-parts make the negative pole of desired size.
The preparation of lithium ion battery:
The LiCoO that is 8:0.5:0.5:1 by weight ratio
2, conductive agent acetylene black, conductive agent carbon black, poly(vinylidene fluoride) (PVDF) joins in N-methyl-pyrrolidone (NMP) solvent, after stirring, makes anode sizing agent; Anode sizing agent is coated on aluminium foil equably, rolling formation after drying, cut-parts make the lithium ion cell positive of 53 millimeters (length) * 30 millimeter (wide).
After the lithium ion cell positive that makes, barrier film, negative pole lamination successively is good, include in the square aluminum hull of 55 millimeters * 34 millimeters * 6 millimeters, the ethylene carbonate that will contain the lithium hexafluoro phosphate (LiPF6) of 1 mol/L: methylcarbonate (EC/DMC) is made into electrolytic solution for 1:1:1 by volume, inject electrolytic bath, the sealed cell aluminum hull can make lithium ion battery.
Adopt FeCl
3as source of iron, be mixed with the solution that volumetric molar concentration is 1.0 mol/L.According to FeCl
3the ratio that is 5:1 with the mol ratio of ammonia adds ammoniacal liquor (15 mol/L) in solution, adds and FeCl
3the citric acid that mol ratio is 2:1 stirs.Above-mentioned liquid phase mixture is sprayed in the air of 450 ℃ cracking, form powder body material, then by above-mentioned materials at N
2in atmosphere, 450 ℃ of high-temperature calcinations obtain ferriferous oxide/carbon composite in 1 hour.Through XRD, detect, the crystal mainly contained in matrix material is Fe mutually
3o
4.Through ultimate analysis, wherein the content of carbon is 19 wt%.The X-ray diffracting spectrum of the matrix material that Fig. 6 is the present embodiment acquisition.The scanning electron microscope pattern that Fig. 7 is this material, the part particle of this material has the porous pattern.
Adopt the method identical with embodiment 1 to test the chemical property of this material.Test result shows, the loading capacity first of this material is 1350 mAh/g, and reversible capacity is 980 mAh/g first.After 200 circulations, Capacitance reserve has 810 mAh/g.The cycle performance curve of the matrix material that Fig. 8 is the present embodiment acquisition.
embodiment 5
With FeCl
3as source of iron, it is mixed with to saturated solution, will with FeCl
3the ammoniacal liquor that mol ratio is 6:1 (concentration is 5 mol/L) and and FeCl
3mol ratio be 2:1 citric acid mixes.Above-mentioned liquid phase mixture is sprayed in 500 ℃ of air cracking, obtain ferriferous oxide/carbon composite.
Adopt the identical method of embodiment 1 to be assembled into simulated battery, the chemical property of test iron.
The loading capacity first of this material is 1190 mAh/g, and reversible capacity is 870 mAh/g first, the capacity of 720 mAh/g that still have an appointment after 200 circulations.The cycle performance curve that Fig. 9 is this material.
Adopt the method identical with embodiment 3 to be prepared to negative pole and lithium ion battery to material.
embodiment 6
Adopt ferric sulfate as source of iron, be made into saturated solution.The lauric acid that this solution is heated in 60 ℃ of backward solution to add with the ferric sulfate mol ratio ammoniacal liquor (10 mol/L) that is 1:1 and is 1:1 with the mol ratio of ferric sulfate, after being mixed evenly, to this liquid phase mixture under vacuum condition, at the temperature of-30 ℃, it is carried out to lyophilize, obtain the powder presoma.And then to this presoma at N
2under gas atmosphere, through 550 ℃ of calcinings 1 hour, obtain containing Fe
2o
3, Fe
3o
4matrix material with carbon.
Adopt the identical method of embodiment 1 to be assembled into simulated battery, test the chemical property of this material.The loading capacity first of this material is 1130mAh/g, and reversible capacity is 790 mAh/g first, and after 150 circulations, capacity is about 450 mAh/g.The cyclic curve figure that Figure 10 is this material.
embodiment 7
Adopt FeCl
3as source of iron, be made into the solution that concentration is 2 mol/L.This solution is heated to add and FeCl in 60 ℃ of backward solution
3the ammoniacal liquor that mol ratio is 5:1 (15 mol/L) and and FeCl
3the mol ratio citric acid that is 1:1, after being mixed evenly, to this liquid phase mixture in air atmosphere at the temperature of 600 ℃ to its cracking of being sprayed, obtain the powder presoma.And then to this presoma at N
2under gas atmosphere, through 500 ℃ of calcinings 0.5 hour, obtain ferriferous oxide/carbon composite.
Adopt the identical method of embodiment 1 to be assembled into simulated battery, test the chemical property of this material.The loading capacity first of this material is 1200 mAh/g, and reversible capacity is 870 mAh/g first, and after 150 circulations, capacity is about 620 mAh/g.The cyclic curve figure that Figure 11 is this material.
With FeCl
3for source of iron, by FeCl
3be mixed with saturated solution, will with FeCl
3ammoniacal liquor (concentration is 15 mol/L) and citric acid that mol ratio is respectively 3.5:1 and 1:1 add the above-mentioned FeCl that is 80 ℃ to Heating temperature to
3in solution, mix.This liquid phase mixture is carried out to spraying drying.Drying temperature is 200 ℃.The powder that drying is obtained under nitrogen protection 400 ℃ the calcining 3 hours, obtain amorphous iron oxide/carbon matrix material.Content to carbon in matrix material adopts elemental microanalysis method to be analyzed, and in matrix material, the content of carbon is 29 wt%.
The scanning electron microscope pattern that Figure 12 is this matrix material.
The x-ray diffraction pattern that Figure 13 is this matrix material, this matrix material is amorphous phase as seen.
The x-ray photoelectron spectroscopy figure that Figure 14 is this matrix material, exist iron and oxygen element in matrix material, wherein iron is mixed valence.
The transmission electron microscope picture that Figure 15 is this matrix material.Zone relatively dark in figure is ferriferous oxide, and the zone of light color is carbon relatively.The diffractogram that diffractogram in figure is the amorphous iron oxide compound.
Adopt the identical method of embodiment 1 to be assembled into simulated battery, test the chemical property of this material.The cyclic curve figure that Figure 16 is this material.The loading capacity first of this material is 1310 mAh/g, and reversible capacity is 850 mAh/g first, and after 200 circulations, capacity is about 800 mAh/g, almost not decline.Matrix material has excellent cycle performance.
Adopt the method identical with embodiment 1 that this amorphous Fe oxide/carbon matrix material is prepared into to negative pole and lithium ion battery.
Adopt iron protochloride as source of iron, be made into the solution that concentration is 1 mol/L.The glucose that this solution is heated in 60 ℃ of backward solution to add with the iron protochloride mol ratio ammoniacal liquor (10 mol/L) that is 2:1 and is 6:1 with the mol ratio of iron protochloride, after being mixed evenly, this liquid phase mixture is carried out to spraying drying to it in air atmosphere at the temperature of 200 ℃, obtain the powder presoma.And then to this presoma under Ar gas atmosphere, through 500 ℃ of calcinings 3 hours, obtain ferriferous oxide/carbon composite, in matrix material, the content of carbon is 70% of matrix material mass percent.
Adopt the identical method of embodiment 1 to be assembled into simulated battery, test the chemical property of this material.The loading capacity first of matrix material is 1020 mAh/g, and reversible capacity is 720 mAh/g first, and after 50 circulations, capacity is 480 mAh/g.
Adopt FeCl
3as source of iron, it is mixed with to the solution that concentration is 1.5 mol/L.In solution, add and FeCl
3the ammoniacal liquor that mol ratio is 3:1 (5 mol/L) and and FeCl
3the mol ratio polyvinyl alcohol that is 0.5:1, after being mixed evenly, this liquid phase mixture is carried out to spraying drying to it in air atmosphere at the temperature of 150 ℃, the product obtained is ground, obtain the powder presoma.And then to this presoma at N
2under gas atmosphere, through 700 ℃ of calcinings 1 hour, obtain ferriferous oxide/carbon composite.The content of matrix material carbon is 15% of matrix material mass percent.
Adopt the identical method of embodiment 1 to be assembled into simulated battery, the loading capacity first of testing the chemical property matrix material of this material is 990 mAh/g, and reversible capacity is 710 mAh/g first, and after 50 circulations, capacity is 510 mAh/g.
embodiment 11
Adopt FeCl
3as source of iron, it is mixed with to the solution that concentration is 1.0 mol/L.In solution, add and FeCl
3the ammoniacal liquor that mol ratio is 3:1 (5 mol/L) and and FeCl
3the mol ratio lauric acid that is 0.3:1, after being mixed evenly, this liquid phase mixture is carried out to spraying drying to it in air atmosphere at the temperature of 150 ℃, the product obtained is ground, obtain the powder presoma.And then to this presoma under hydrogen atmosphere, through 600 ℃ of calcinings 1 hour, obtain ferriferous oxide/carbon composite.The content of matrix material carbon is 11% of matrix material mass percent.
Adopt the identical method of embodiment 1 to be assembled into simulated battery, the loading capacity first of testing the chemical property matrix material of this material is 1010 mAh/g, and reversible capacity is 780 mAh/g first, and after 50 circulations, capacity is 668 mAh/g.
embodiment 12
The employing iron protochloride as source of iron, is mixed with by it solution that concentration is 2.0 mol/L as source of iron.In solution, add and FeCl
3the ammoniacal liquor that mol ratio is 3:1 (5 mol/L) and and FeCl
3the mol ratio citric acid that is 0.5:1, after being mixed evenly, this liquid phase mixture is carried out to spraying drying to it in air atmosphere at the temperature of 200 ℃, the product obtained is ground, obtain the powder presoma.And then to this presoma under the mixed atmosphere of nitrogen and 10% hydrogen (volume ratio), through 550 ℃ of calcinings 2 hours, obtain ferriferous oxide/carbon composite.
Adopt the identical method of embodiment 1 to be assembled into simulated battery, the loading capacity first of testing the chemical property matrix material of this material is 970 mAh/g, and reversible capacity is 752 mAh/g first, and after 50 circulations, capacity is 516 mAh/g.
Claims (11)
1. the preparation method of a ferriferous oxide/carbon composite, is characterized in that the method comprises the following steps:
1) take water-soluble molysite as source of iron, take the Water Soluble Organic Carbon source as carbon source, molysite aqueous solution and ammoniacal liquor and organic carbon source are mixed, obtain liquid phase mixture;
2) to this liquid phase mixture, adopt the method for spraying drying, lyophilize or spraying cracking to form the powder presoma, then this presoma is calcined, be prepared into ferriferous oxide/carbon composite; Perhaps, directly to the cracking of being sprayed of this mixing solutions, be prepared into ferriferous oxide/carbon composite; 5～70 wt% that in described ferriferous oxide/carbon composite, the content of carbon is the matrix material mass percent, preferably the content of carbon is 20～60% of matrix material mass percent, one or more in the amorphous compound that described ferriferous oxide is iron and oxygen, FeO, Fe3O4, Fe2O3.
2. the preparation method of ferriferous oxide/carbon composite according to claim 1, it is characterized in that: water-soluble molysite is one or more mixing in iron trichloride, iron protochloride, ironic oxalate, iron nitrate, ferric sulfate and ferrous sulfate and their crystalline hydrate, is preferably lower-cost iron trichloride or its crystalline hydrate.
3. the preparation method of ferriferous oxide/carbon composite according to claim 1, it is characterized in that: the Water Soluble Organic Carbon source adopted is one or more in citric acid, lauric acid, sucrose, glucose and polyvinyl alcohol.
4. the preparation method of ferriferous oxide/carbon composite according to claim 1, the mol ratio that it is characterized in that water-soluble molysite and ammoniacal liquor is 1:(0.2 ~ 20), be preferably 1:(1 ~ 5); The mol ratio in water-soluble molysite and Water Soluble Organic Carbon source is 1:(0.2 ~ 8), be preferably 1:(0.5 ~ 5); The saturated volumetric molar concentration that the volumetric molar concentration of water-soluble molysite is 0.5 mol/L～water-soluble molysite, the concentration of ammoniacal liquor is 3～15 mol/L.
5. the preparation method of ferriferous oxide/carbon composite according to claim 1 is characterized in that: liquid phase mixture adopts spraying drying to prepare the powder presoma, and drying temperature is 100～500 ℃, preferably 150～400 ℃; Dry atmosphere can adopt the mixed gas of air, nitrogen, argon gas or above one or more gases, is preferably air; Then, the powder presoma that drying is obtained is calcined, and calcining temperature is 300～900 ℃, is preferably 350～700 ℃; Calcination atmosphere can adopt the mixed gas of air, nitrogen, argon gas, hydrogen, methane, ammonia or above one or more gases; The time of calcining is 0.5 ~ 6 hour, is preferably 1 ~ 4 hour.
6. the preparation method of ferriferous oxide/carbon composite according to claim 1, it is characterized in that: liquid phase mixture is under the mixed gas of air, nitrogen, argon gas or above one or more gases, the cracking of spraying under 300～900 ℃, directly form ferriferous oxide/carbon composite; As preferably, the spraying cracking temperature is 350～800 ℃, and cracking atmosphere adopts air.
7. the preparation method of ferriferous oxide/carbon composite according to claim 1, it is characterized in that: liquid phase mixture is sprayed and is cracked into the powder presoma under 100～500 ℃ at the mixed gas of air, nitrogen, argon gas or above one or more gases, and then under 300～900 ℃, calcine in inert atmosphere 0.5～6 hour, form ferriferous oxide/carbon composite; The mixed gas that inert atmosphere is nitrogen, argon gas or nitrogen and argon gas; As preferably, cracking atmosphere adopts air; As preferably, calcination atmosphere adopts nitrogen, and calcination time is 1 ~ 4 hour.
8. the preparation method of ferriferous oxide/carbon composite according to claim 1 is characterized in that: liquid phase mixture adopts lyophilize to prepare the powder presoma,, drying temperature be-10～-70 ℃, is preferably-20～-50 ℃, and the employing dynamic vacuum; Then, the powder presoma that drying is obtained is calcined, and calcining temperature is 300～900 ℃, is preferably 350～700 ℃; Calcination atmosphere can adopt the mixed gas of air, nitrogen, argon gas, hydrogen, methane, ammonia or above one or more gases; The time of calcining is 0.5 ~ 6 hour, is preferably 1 ~ 4 hour.
9. ferriferous oxide/the carbon composition lithium ion battery cathode material prepared according to the described method of claim 1～8.
10. lithium ion battery negative, it is characterized in that: adopt negative material claimed in claim 9 and binding agent, conductive agent to be mixed to form slurry in solvent, slurry is coated to Copper Foil, foam copper or nickel foam collection liquid surface, after oven dry and compacting, obtains lithium ion battery negative.
11. lithium ion battery is characterized in that: this lithium ion battery adopts the anodal and in-between barrier film of negative pole claimed in claim 10, removal lithium embedded and the lithium ion battery that electrolytic solution forms.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102208614A (en) * | 2011-04-26 | 2011-10-05 | 中国矿业大学 | Method for preparing lithium ion battery cathode material coated iron sesquioxide |
| CN102786097A (en) * | 2012-07-26 | 2012-11-21 | 天津大学 | Hydrothermal preparation method for carbon cladded nanometer ferriferrous oxide particles |
| CN102951687A (en) * | 2012-03-01 | 2013-03-06 | 纳米籽有限公司 | Ferric oxide mesoporous microsphere and preparation method thereof |
| CN103000902A (en) * | 2012-11-20 | 2013-03-27 | 江苏科捷锂电池有限公司 | Preparation method of Si-C composite negative electrode material of lithium ion battery |
| CN103227324A (en) * | 2013-04-24 | 2013-07-31 | 北京科技大学 | Preparation method of iron oxide cathode material for lithium ion battery |
-
2013
- 2013-08-07 CN CN201310341332.1A patent/CN103435105B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102208614A (en) * | 2011-04-26 | 2011-10-05 | 中国矿业大学 | Method for preparing lithium ion battery cathode material coated iron sesquioxide |
| CN102951687A (en) * | 2012-03-01 | 2013-03-06 | 纳米籽有限公司 | Ferric oxide mesoporous microsphere and preparation method thereof |
| CN102786097A (en) * | 2012-07-26 | 2012-11-21 | 天津大学 | Hydrothermal preparation method for carbon cladded nanometer ferriferrous oxide particles |
| CN103000902A (en) * | 2012-11-20 | 2013-03-27 | 江苏科捷锂电池有限公司 | Preparation method of Si-C composite negative electrode material of lithium ion battery |
| CN103227324A (en) * | 2013-04-24 | 2013-07-31 | 北京科技大学 | Preparation method of iron oxide cathode material for lithium ion battery |
Non-Patent Citations (1)
| Title |
|---|
| 何阳等: ""碳纳米管/Fe304纳米复合负极材料的制备与储锂性能研究"", 《第28届全国化学与物理电源学术年会 论文集》 * |
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