CN102244238B - Graphene-like coated iron-based compound doped cathode material and preparation method thereof - Google Patents
Graphene-like coated iron-based compound doped cathode material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a graphene-like coated iron-based compound doped cathode material and a preparation method thereof. The composite powder can be used as the cathode material of a lithium ion battery. The preparation method comprises the following steps: A, uniformly mixing the solution containing liquid oligoacrylonitrile and ferric oxide powder; and drying and curing at a low temperature to obtain a precursor; and B, grinding and crushing the precursor obtained in the step A, and performing the processes of high-temperature sintering and the like to obtain the graphene-like coated iron-based material doped composite powder with multiple components. The preparation method disclosed by the invention has low cost, is easy to operate and can prepare the graphene-like coated composite material doped with a single or multi-component iron-based material disclosed by the invention; and the lithium ion battery made from the composite material has large charge/discharge capacity and excellent high-rate charge/discharge performance.
Description
Technical field
The present invention relates to lithium ion battery material field, particularly a kind of lithium ion battery cathode material and its preparation method.
Background technology
Lithium ion battery energy density is high, quality light, long service life, is a kind of very promising new forms of energy, particularly in removable application, such as: notebook computer, camera, mobile phone etc.Since Sony company in 1991 first by its commercialization, the negative material of business-like secondary lithium battery is all to make negative pole with graphite, it has high coulombic efficiency (> 90 %), but theoretical capacity is relatively low, specific capacity requirement lithium ion battery being increased sharply in order to meet various applications, explore new, more the negative material of high power capacity has become the key issue of development lithium ion battery.
Ferrous oxide is exactly a kind of cathode material for high capacity lithium ion battery, and its theoretical capacity is than high 2 ~ 3 times of (Fe of graphitic carbon
2o
3, Fe
3o
4, FeO theoretical capacity be respectively 1007 mA h g
-1, 926 mA h g
-1with 744 mA h g
-1), safe (can avoid the formation of Li dendrite), and transition metal oxide nano-particles can also improve performance of lithium ion battery by intensifier electrode surface electrochemistry reactivity, and iron oxide is abundant at earth reserves, wide material sources, with low cost, little to environmental pressure, be a kind of desirable active electrode material.
But directly use nano oxidized iron particle to do lithium ion battery, be accompanied by large change in volume in lithium insertion process, the decomposition of iron oxide negative material and pulverizing constantly occur, and finally cause continuous capacity attenuation.In order to improve the chemical property of iron oxide electrode; people are usually by iron oxide particles and carbon compound use; be because carbon-coating can well be protected inner negative electrode active electrode material as barrier, suppress the change in volume of negative material, and maintain their high power capacity.
Traditional carbon coating-doping iron oxide composite granule of preparing is to utilize physical means as arc-discharge technique, laser evaporation method, chemical deposition, the decomposition of metallorganic direct heat etc.; these methods often can be used poisonous or expensive precursor and high boiling organic solvent; and the equipment using is complicated, power consumption is large, cost is high, complex operation, reaction are violent, thereby be difficult to realize large-scale production.These reactions often can only obtain the primary product of single iron oxide component, are difficult to regulate and control product component; And the carbon obtaining is impalpable structure mostly, its chemical property is relatively poor.
Therefore, prior art has yet to be improved and developed.
Summary of the invention
Kind graphene coated doping iron based compound negative material of the present invention and preparation method thereof, object is to overcome decomposition and the pulverizing that iron oxide negative material constantly occurs in prior art, and the technological deficiency that causes continuous battery capacity to decay, aim to provide a kind of low cost, simple class graphene coated doping iron based compound composite granule as lithium ion battery negative material, to solve existing problem in prior art.
Technical scheme of the present invention is as follows:
The preparation method of one kind graphene coated doping iron based compound negative material, wherein, comprises the following steps:
A, alpha-iron oxide nano-powder is mixed in certain mass ratio with oligoacrylonitrile, grind it is mixed, more than 180 ℃ isothermal curing 2 ~ 4 hours, obtain presoma;
B, the presoma obtaining in steps A is ground after, under inert atmosphere protection, first 300 ℃ of calcinings 1 hour, then continue to be warming up to 500 ℃ of above calcinings 1 ~ 8 hour, make the multiple iron series compound composite granule of class graphene coated doping.
The preparation method of described class graphene coated doping iron based compound negative material, wherein, nano-sized iron oxide described in steps A is Fe
3o
4,
γ-Fe
2o
3or
α-Fe
2o
3.
The preparation method of described class graphene coated doping iron based compound negative material, wherein, in mass ratio, oligoacrylonitrile: nano-sized iron oxide is 0.05 ~ 0.2: 1.
The preparation method of described class graphene coated doping iron based compound negative material, wherein, the curing temperature described in steps A is 180 ~ 240 ℃.
The preparation method of described class graphene coated doping iron based compound negative material, wherein, described oligoacrylonitrile is liquid, relative molecular weight is 106 ~ 5000.
The preparation method of described class graphene coated doping iron based compound negative material, wherein, the grinding in preparation method described in step B adopts planetary ball mill to grind.
The preparation method of described class graphene coated doping iron based compound negative material, wherein, in step B, inert atmosphere is nitrogen or argon gas during sintering.
The preparation method of described class graphene coated doping iron based compound negative material, wherein, in step B, first 300 ℃ of calcinings 1 hour, then continues to be warming up to 500 ~ 800 ℃ of calcinings 4 ~ 6 hours.
The class graphene coated doping iron based compound negative material that the preparation method of the class graphene coated doping iron based compound negative material described in applying makes, wherein, on iron series compound surface, coating-doping has class graphene layer.
Adopt technique scheme, kind graphene coated doping iron based compound negative material provided by the present invention and preparation method thereof, on iron series compound surface, limits the change in volume of iron series compound in charge and discharge cycles by class graphene coated on the one hand; On the other hand, class Graphene can play obstruct electrolyte and contact with iron series compound, thereby reduces irreversible reaction; And without using any organic solvent, with low cost, simple to operate, can prepare the single or multicomponent iron series compound composite granule of class graphene coated doping.
Accompanying drawing explanation
Fig. 1 is the XRD collection of illustrative plates (X ray diffracting spectrum) of embodiment 1 prepared product.
Fig. 2 is the XRD collection of illustrative plates of embodiment 2 prepared products.
Fig. 3 is the XRD collection of illustrative plates of embodiment 3 prepared products.
Fig. 4 is the XRD collection of illustrative plates of embodiment 4 prepared products.
Embodiment
The invention provides kind graphene coated doping iron based compound negative material and preparation method thereof, for making object of the present invention, technical scheme and effect clearer, clear and definite, below the present invention is described in more detail.Should be appreciated that specific embodiment described herein, only in order to explain the present invention, is not intended to limit the present invention.
Class graphene coated doping iron based compound composite granule of the present invention comprises Fe
3-xo
4/ C, Fe
3-xo
4/ Fe/C and Fe
3-xo
4tri-kinds of composite granules of/FeO/C, wherein C represents class graphite olefinic carbon.
The preparation method of class graphene coated doping iron based compound negative material of the present invention, comprises the following steps:
A, by commercially available or mix in certain mass ratio with oligoacrylonitrile with the homemade alpha-iron oxide nano-powder of coprecipitation, grind it mixed, more than 180 ℃ isothermal curing 2 ~ 4 hours, obtain presoma.
B, the presoma obtaining in steps A is ground after; under inert atmosphere protection; first 300 ℃ of calcinings 1 hour; then continue to be warming up to 500 ℃ of above calcination 1 ~ 8 hour; be preferably calcining 4 ~ 6 hours; oligoacrylonitrile forms class graphene layer between iron oxide particles surface and particle through sintering, simultaneously to nano oxidized iron particle partial reduction, make the multiple iron series compound composite granule of class graphene coated doping.
Nano-sized iron oxide of the present invention is Fe
3o
4,
γ-Fe
2o
3or
α-Fe
2o
3, Fe wherein
3o
4with
γ-Fe
2o
3do not distinguish, use Fe
3-xo
4represent.
In preparation method's of the present invention steps A in mass ratio, oligoacrylonitrile: iron oxide is 0.05 ~ 0.2: 1.
Curing temperature described in preparation method's of the present invention steps A is 180 ~ 240 ℃.
Grinding described in preparation method's of the present invention step B adopts planetary ball mill to grind, and in the presoma that guarantees to prepare, each component mixes, and reduces the particle diameter of compound particle.
The present invention's carbon precursor used oligoacrylonitrile is liquid, and relative molecular weight is 106 ~ 5000.
The calcined product of the present invention's oligoacrylonitrile used is class graphene-structured, and there is the effect of reducing agent, when oligoacrylonitrile when calcining under inert atmosphere, on alpha-iron oxide nano-powder surface, form class graphene layer, have compared with strong reducing property, and its thermal decomposition also can produce CO, H
2reducibility gas, can reduce nano-sized iron oxide.
During sintering of the present invention, inert atmosphere is nitrogen or argon gas, calcining is divided into two stages, and the calcining heat of first stage is 300 ℃, and main purpose is to make the preliminary carbonization of oligoacrylonitrile, structure is further stable, reduces its mass loss under high temperature sintering; Second stage calcination temperature is 500 ~ 800 ℃, and oligoacrylonitrile is converted to class graphene-structured completely, and the class Graphene of formation is complete is coated on iron series compound surface.
The composite granule of the class graphene coated doping iron based compound that the preparation method of class graphene coated doping iron based compound negative material of the present invention makes, wherein, is coated with class graphene layer on iron series compound surface.
Iron series compound of the present invention comprises Fe
3-xo
4, FeO, Fe.
Beneficial effect of the present invention:
1) kind graphene coated doping iron based compound negative material provided by the present invention and preparation method thereof, adopt simple solid-liquid mixing method, complete in two steps the preparation of composite granule, A step mixes with nano-sized iron oxide propylene liguid nitrile oligomer carbon source at molecular level, the cured product obtaining in low-temperature decomposition is distributed in nano-sized iron oxide intercrystalline and grain surface preferably, B step is ground by planetary ball mill, the dispersiveness that makes the curing presoma obtaining keep little particle diameter to become reconciled, and the calcining of B step is divided into two stages, first stage, 300 ℃ of calcinings made the preliminary carbonization of oligoacrylonitrile, structure is further stable, reduce its mass loss under high temperature sintering, second stage calcining is that oligoacrylonitrile is converted to class graphene-structured completely, and the class Graphene of formation is complete is coated on iron series compound surface, and whole preparation technology is simple to operate, with low cost, has greatly improved production efficiency.
2) class graphene coated doping iron based compound negative material provided by the present invention and preparation method thereof, on iron series compound surface, limits the change in volume of iron series compound in charge and discharge cycles by class graphene coated on the one hand; On the other hand, class Graphene can play obstruct electrolyte and contact with iron series compound, thereby reduces irreversible reaction; Last class Graphene doping is coated is that the conductivity of composite granule is significantly improved; Thereby use the chemical property of the lithium ion battery that this material makes very excellent.
Be the non-limiting preparation case of the present invention below, by these embodiment, the invention will be further described.
Embodiment 1:
(1) take the self-control iron oxide Fe that 1 g particle diameter is 16 nm
3-xo
4powder and 0.05 g oligoacrylonitrile ground and mixed, under 220 ℃ of air atmosphere, isothermal curing obtains presoma for 2 hours.
(2) presoma obtaining in step (1) is adopted to planetary ball mill; ratio of grinding media to material is 10: 1; 400 r/min ball millings are after 24 hours, under nitrogen protection, first 300 ℃ of calcinings 1 hour; then continue to be warming up to 500 ℃ of temperature sintering 8 hours; oligoacrylonitrile forms class graphene coated layer through sintering at particle surface, and owing to adding oligoacrylonitrile less, sintering time is shorter; not by Reduction of Oxide Cheng Tie, thereby make Fe
3-xo
4/ C composite granule.
Embodiment 2:
(1) take the iron oxide Fe that 1 g particle diameter is 20 nm
3-xo
4powder and 0.12 g oligoacrylonitrile ground and mixed, under 180 ℃ of air atmosphere, isothermal curing obtains presoma for 4 hours.
(2) presoma obtaining in step (1) is adopted to planetary ball mill; ratio of grinding media to material is 10: 1; 400 r/min ball millings are after 24 hours; under nitrogen protection; first 300 ℃ of calcinings 1 hour; then continue to be warming up to 600 ℃ of temperature sintering 6 hours, oligoacrylonitrile forms class graphene coated layer through sintering at particle surface, and by minority Fe
3-xo
4be reduced into simple substance
α-Fe, obtains Fe
3-xo
4/ Fe/C composite granule.
Embodiment 3:
(1) taking commercially available particle diameter is 250 nm iron oxide
α-Fe
2o
3powder 2 g and oligoacrylonitrile 0.4 g ground and mixed are even, and under 180 ℃ of air atmosphere, isothermal curing obtains presoma for 4 hours.
(2) presoma obtaining in step (1) is adopted to planetary ball mill; ratio of grinding media to material is 10: 1; 400 r/min ball millings are after 24 hours; under argon shield; first 300 ℃ of calcinings 1 hour; then continue to be warming up to 700 ℃ of sintering 2 hours, oligoacrylonitrile forms class graphene coated layer through sintering at particle surface, and will
α-Fe
2o
3restore All becomes Fe
3-xo
4, obtain Fe
3-xo
4/ C composite granule.
Embodiment 4:
(1) take the iron oxide Fe that particle diameter is 20 nm
3-xo
4powder 40 g and oligoacrylonitrile 6 g, ground and mixed is even, then at 220 ℃ of isothermal curings, within 3 hours, obtains presoma.
(2) presoma obtaining in step (1) is adopted to planetary ball mill; ratio of grinding media to material is 10: 1; 400 r/min ball millings are after 24 hours; under argon shield; first 300 ℃ of calcinings 1 hour; then continue to be warming up to 800 ℃ of sintering 1 hour, oligoacrylonitrile forms class graphene coated layer through sintering at particle surface, and by part Fe
3-xo
4be reduced into FeO and simple substance
α-Fe, obtains Fe
3-xo
4/ FeO/ Fe/ C composite granule.
Embodiment 5:
(1) take the iron oxide Fe that particle diameter is 20 nm
3-xo
4powder 40 g and oligoacrylonitrile 6 g, after ground and mixed is even, obtain presoma for 2 hours at 240 ℃ of isothermal curings.
(2) by the presoma obtaining in step (1); adopt planetary ball mill; ratio of grinding media to material is 10: 1; 400 r/min ball millings are after 24 hours; under argon shield, first, 300 ℃ of calcinings 1 hour, then continue to be warming up to 600 ℃ of sintering 4 hours; oligoacrylonitrile forms class graphene coated layer through sintering at particle surface, and by part Fe
3-xo
4be reduced into simple substance
α-Fe, obtains Fe
3-xo
4/ Fe/ C composite granule.
Above 5 embodiment illustrate the preparation of class graphene coated doping iron based compound negative material provided by the present invention.
Comprehensive embodiment 1 ~ 5, further test.
(1) preparation of battery
The preparation of electrode to be measured
The positive active material LiMn2O4 composite powder material respectively 0.4 g being made by embodiment 1 ~ 5,0.05 g binding agent Kynoar (PVDF) and 0.05 g conductive agent acetylene black mixed grinding are even, add 5 g 1-METHYLPYRROLIDONEs, stir and form uniform sizing material.
This slurry is coated in uniformly on the Copper Foil of 20 microns, then at 65 ℃, dries, punching, making diameter is the electrode disk of 14 mm, wherein containing having an appointment 1.5 mg active materials.
Electrode is adopted to commercially available lithium ion battery specialized lithium sheet.
The assembling of battery
Adopt 2032 type button cell test material performances, assemble sequence is negative electrode casing-shell fragment-pad-lithium sheet-electrolyte-barrier film-electrolyte-positive plate-pad-anode cover, then will assemble battery and encapsulate, and whole process all completes in glove box.
(2) battery performance test
Cycle performance test: the above-mentioned 2032 type lithium ion batteries that make are placed on respectively on test macro, after standing 1 minute, first with 0.1 C, carry out constant-current discharge to lower voltage limit 0.02 V, standing 1 minute again, then with 0.1 C constant current charge to 3.0 V, then repeat after above-mentioned steps 50 times, record battery discharge capacity now, by following formula calculated capacity conservation rate:
Capability retention=(the 50th cyclic discharge capacity/for the second time cyclic discharge capacity) * 100 %, do not adopt discharge capacity calculated capacity conservation rate for the first time, because its irreversibility is very large, influencing factor is numerous, therefore select cyclic discharge capacity for the second time to make calculated capacity conservation rate, more can reflect battery intrinsic performance.
Heavy-current discharge performance test:
By the battery through after 0.1 C electric current charge and discharge cycles 50 times, and then successively with 1 C, 2 C and each charge and discharge cycles of 5 C electric currents 20 times, record the discharge capacity after each high current charge-discharge circulation of battery 20 times.
Result is as shown in table 1 below, and wherein comparative example 1 is the self-control iron oxide Fe of 16 nm by pure phase particle diameter
3-xo
4the lithium battery that powder is made as Electrode, comparative example 2 for pure phase particle diameter be 250 nm iron oxide
α-Fe
2o
3the lithium battery that powder is made as Electrode.
Table 1
Product in above-described embodiment is characterized through XRD, and concrete outcome is as follows.
Fig. 1 is the XRD collection of illustrative plates of embodiment 1 prepared product.In Fig. 1, abscissa is angle of diffraction 2-Theta(degree), ordinate is intensity I ntensity(a. u.); Phase is the Fe of cubic system
3o
4or γ-Fe
2o
3, due to Fe
3o
4and γ-Fe
2o
3all also suitable (Fe of spinel structure and lattice constant a
3o
4be 0.8396 nm, γ-Fe
2o
3be 0.8346 nm), its difference is very difficult to be judged by XRD collection of illustrative plates, the present invention does not distinguish these two kinds of materials, unification Fe
3-xo
4represent.
Fig. 2 be embodiment 2 prepared products XRD collection of illustrative plates.In figure, the peak of arrow indication is the diffraction maximum of simple substance α-Fe, and other peaks are Fe
3-xo
4peak.
Fig. 3 is the XRD collection of illustrative plates of embodiment 3 prepared products.In figure, be phase Fe
3-xo
4diffraction maximum, show
α-Fe
2o
3be reduced to Fe completely
3-xo
4.
Fig. 4 is the XRD collection of illustrative plates of embodiment 4 prepared products.In figure, each symbol of institute's mark represents respectively: (●) Fe
3-xo
4, (zero)
α-Fe, (△) FeO, contains Fe in iron series compound in the composite granule that shows to prepare
3-xo
4, FeO,
αtri-kinds of phases of-Fe.
Data from table 1 can find out, the battery discharge specific capacity that the coated iron series compound composite granule of class Graphene doping being prepared by the inventive method is made is higher, through 50 charge and discharge cycles capacity of 0.1 C electric current, also all remains on 245 mA h g
-1above, have even up to 584 mA h g
-1, this is far above the capacity of commercial carbon-based material of present stage, and its high rate charge-discharge performance is also comparatively excellent, far away higher than pure phase nanometer Fe
3-xo
4and nanometer
α-Fe
2o
3material.
From the result of above-described embodiment, under different reaction conditions, can obtain the iron series compound composite granule of the coated different component of class Graphene doping: Fe
3-xo
4/ C, Fe
3-xo
4/ Fe/C and Fe
3-xo
4/ FeO/Fe/C, this synchronous reduction and class graphene coated preparation method, can change the existence of fe in its chemical property, particularly iron series compound by the component of regulation and control product, improved greatly the conductivity of active material.
Should be understood that, application of the present invention is not limited to above-mentioned giving an example, and for those of ordinary skills, can be improved according to the above description or convert, and all these improvement and conversion all should belong to the protection range of claims of the present invention.
Claims (5)
1. the preparation method of a kind graphene coated doping iron based compound negative material, is characterized in that, comprises the following steps:
A, alpha-iron oxide nano-powder is mixed in certain mass ratio with oligoacrylonitrile, grind it is mixed, more than 180 ℃ isothermal curing 2 ~ 4 hours, obtain presoma;
B, the presoma obtaining in steps A is ground after, under inert atmosphere protection, first 300 ℃ of calcinings 1 hour, then continue to be warming up to 500 ~ 800 ℃ of calcinings 4 ~ 6 hours, make the multiple iron series compound composite granule of class graphene coated doping;
Nano-sized iron oxide described in steps A is Fe
3o
4,
γ-Fe
2o
3or
α-Fe
2o
3;
In mass ratio, oligoacrylonitrile: nano-sized iron oxide is 0.05 ~ 0.2: 1.
2. the preparation method of class graphene coated doping iron based compound negative material according to claim 1, is characterized in that, the curing temperature described in steps A is 180 ~ 240 ℃.
3. the preparation method of class graphene coated doping iron based compound negative material according to claim 1, is characterized in that, described oligoacrylonitrile is liquid, and relative molecular weight is 106 ~ 5000.
4. the preparation method of class graphene coated doping iron based compound negative material according to claim 1, is characterized in that, the grinding in preparation method described in step B adopts planetary ball mill to grind.
5. the preparation method of class graphene coated doping iron based compound negative material according to claim 1, is characterized in that, while calcining in step B, inert atmosphere is nitrogen or argon gas.
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| CN110690425B (en) * | 2019-09-29 | 2021-12-07 | 上海应用技术大学 | Boron-doped reduced carbon nanotube-loaded ferric oxide composite material and preparation method thereof |
| CN111952555A (en) * | 2020-07-07 | 2020-11-17 | 华南理工大学 | Lithium ion battery cathode material based on fine iron powder and preparation |
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