CN102339994A - Transition metal oxide/ graphene nanometer composite electrode material used for lithium battery and preparation method thereof - Google Patents
Transition metal oxide/ graphene nanometer composite electrode material used for lithium battery and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a transition metal oxide/ graphene nanometer composite electrode material used for a lithium battery and a preparation method thereof. The transition metal oxide/ grapheme nanometer composite electrode material is the transition metal oxide modified by grapheme or graphene oxide, wherein the transition metal oxide and the grapheme or the graphene oxide can be connected in a physical packaging or chemical bonding mode. One of the following methods is adopted: 1. evenly mixing a precursor and graphene (or graphene oxide) required by preparing the transition metal oxide at the mass ratio of 0.01: 100 to 50: 100 in a solvent, and reacting at a certain temperature and pressure to obtain the nanometer composite electrode material; and 2. fully mixing the graphene (or graphene oxide) and the transition metal oxide at the mass ratio of 0.01: 100 to 50: 100 in a solvent, and drying to obtain the nanometer composite electrode material. The preparation method is simple, is easy to operate and is suitable for large-scale production, the prepared electrode material has higher lithium-ion and electron conductivity, and the assembled lithium battery has the advantages of high lithium battery specific capacity and good cycle performance and is suitable for the lithium battery electrode material.
Description
Technical field
The invention belongs to the energy storage material technical field, be specifically related to one type of lithium battery with transition metal oxide/Graphene (or graphene oxide) nanometer combined electrode material and preparation method thereof with excellent cycle performance and height ratio capacity.
Background technology
The energy is the material base of human social activity, and the development of the energy and energy and environment are the whole world, whole mankind's questions of common interest.At present, the worsening shortages of the chemical fuel resource in the global range forces people to seek novel alternative clean energy resource.Simultaneously, along with the fast development of information-intensive society, special demand has been proposed for effective, portable energy storage and converting system.These energy systems become the key components of current portable electronic consumer products.And to energy-conservation and position environmental protection, need energy storage system at times and from the natural clean energy resource of solar energy and wind energy.These demands become present research more advanced person, high-energy-density, can discharge and recharge the driving force of battery system.Therefore, development high-performance, low cost, environment protection type battery have become the development priority of battery industry.
Lithium battery has the energy density height, power output is big, and average output voltage is high, self discharge is little, memory-less effect; But fast charging and discharging, cycle performance is superior, and non-environmental-pollution; Become the first-selected object in the chargeable source of current portable type electronic product, be considered to the most promising chemical power source.In lithium battery, electrode material is in occupation of center-stage, and the performance quality of electrode material has directly determined each item performance index of final lithium battery product.Adopt the electrode material of transition metal oxide, have excellent voltage platform and specific capacity as lithium battery.Yet; The oxide material of traditional structure is difficult in specific capacity and there is new breakthrough electrochemistry cycle performance aspect; And structural change owing to the low electronic conductivity of transition metal oxide material itself, low lithium ion diffusion coefficient and host lattice; Cause its cycle performance unsatisfactory, thereby composite material with nanostructure of design and preparation become the effective way of the high-performance lithium battery electrode material of acquisition.
Graphene is a kind of new material that rises rapidly in recent years; As a kind of new allotrope of carbon, have special cellular two-dimensional structure, form by the monolayer carbon atom; It not only has the favorable mechanical performance; Unique chemical property is also arranged, have excellent electronic conductivity, simultaneously lithium ion is also had good conductive performance; Be applied to be expected to realize the quick conduction of electronics and lithium ion in the electrode material of lithium battery and suppress the effect that material structure changes, thereby realize the high performance of lithium battery performance.
Summary of the invention
First technical problem to be solved by this invention provide a kind of widely applicable, prepare easily lithium battery with transition metal oxide/graphene nano combination electrode material, the battery specific capacity of its assembling is big, good cycle.
Second technical problem to be solved by this invention provides the preparation method of a kind of lithium battery with transition metal oxide/graphene nano combination electrode material.
The present invention solves the technical scheme that above-mentioned first technical problem takes: a kind of lithium battery is with transition metal oxide/graphene nano combination electrode material; It is characterized in that this lithium battery uses the transition metal oxide of transition metal oxide/graphene nano combination electrode material as Graphene or graphene oxide modification; Said Graphene or graphene oxide are connected with the mode of transition metal oxide through physics parcel or chemical bonding, and wherein the mass ratio of Graphene or graphene oxide and transition metal oxide is 0.01: 100～50: 100.
As preferably, said transition metal oxide is the oxide of manganese, comprises manganese dioxide, manganese sesquioxide managnic oxide, mangano-manganic oxide or the embedding lithium manganese oxide of different crystal forms; The oxide of vanadium comprises α phase, amorphous vanadic oxide or embedding lithium-barium oxide; The oxide of iron comprises FeOOH, magnetic iron ore tri-iron tetroxide or bloodstone α-di-iron trioxide; The oxide of chromium comprises chrome green, chromium dioxide, five oxidations, two chromium, 15 oxidations, six chromium or eight oxidations, three chromium; The oxide of molybdenum comprises molybdenum trioxide, 11 oxidations, four molybdenums, 23 oxidations, eight molybdenums or 26 oxidations, nine molybdenums; Perhaps some other transition metal oxide and embedding lithium oxide thereof are like cupric oxide, nickel oxide and cobalt oxide, lithium and cobalt oxides, lithium nickel oxide etc.
Said Graphene is individual layer or is made up of the two-dimentional lonsdaleite material of the number of plies between one to three layer that graphene oxide is to contain hydroxyl or carboxyl or epoxy radicals on the Graphene.
Said lithium battery is used as positive electrode active materials or negative active core-shell material with transition metal oxide/graphene nano combination electrode material in lithium battery.Distinguish according to the transition metal oxide self character is different with the voltage range that discharges and recharges.
The present invention solves the technical scheme that above-mentioned second technical problem take: a kind of lithium battery is characterized in that with the preparation method of transition metal oxide/graphene nano combination electrode material step is:
The precursor that Graphene or graphene oxide and preparation transition metal oxide is required is in solvent, evenly to mix in 0.01: 100～50: 100 by mass ratio; Place autoclave; Reaction is more than 1 hour under 60～300 ℃ of conditions, and the lithium battery that obtains chemical bonding is with transition metal oxide/graphene nano combination electrode material; Be in solvent, fully to mix in 0.01: 100～50: 100 Graphene or graphene oxide and transition metal oxide by mass ratio perhaps, the lithium battery that obtains the physics parcel through dried is with transition metal oxide/graphene nano combination electrode material.
The required precursor of said preparation transition metal oxide is meant required slaine and oxidant or the reducing agent of preparation transition metal oxide.
As preferably, said transition metal oxide is the oxide of manganese, comprises manganese dioxide, manganese sesquioxide managnic oxide, mangano-manganic oxide or the embedding lithium manganese oxide of different crystal forms; The oxide of vanadium comprises α phase, amorphous vanadic oxide or embedding lithium-barium oxide; The oxide of iron comprises FeOOH, magnetic iron ore tri-iron tetroxide or bloodstone α-di-iron trioxide; The oxide of chromium comprises chrome green, chromium dioxide, five oxidations, two chromium, 15 oxidations, six chromium or eight oxidations, three chromium; The oxide of molybdenum comprises molybdenum trioxide, 11 oxidations, four molybdenums, 23 oxidations, eight molybdenums or 26 oxidations, nine molybdenums; Perhaps some other transition metal oxide and embedding lithium oxide thereof.
As improvement, said mixed media is mechanical agitation, ball milling, the one or more combination in ultrasonic, and incorporation time is 0.5-30 hour.
Improve, said solvent is water, ethanol, acetone, dimethyl sulfoxide (DMSO), N, dinethylformamide, oxolane, chloroform, carbon tetrachloride or dichloro-benzenes again.
At last, said dry means are spray drying or direct drying.
Compared with prior art; The invention has the advantages that: utilize the unique chemical property of Graphene, promptly have excellent electronics and ionic conductivity, be applied to also can suppress in the electrode material of lithium battery structural change of material; There are very strong physics parcel or chemical bonding between prepared transition metal oxide and the Graphene (or graphene oxide); Overcome the fluffy shortcoming with the transition metal oxide structural change of nano material volume, improved tap density and cycle performance, unique conductive network is provided simultaneously; Improve electronic conductivity, reduced the internal resistance of battery.The preparation method that the present invention adopted is easy, easy to operate, is applicable to large-scale production, and prepared electrode material has the conductivity of higher lithium ion and electronics, adopts the battery specific capacity of this type of electrode material assembling high, and cycle performance is excellent.
Description of drawings
Fig. 1 is the sem photograph of the prepared manganese dioxide/graphene oxide combination electrode material of embodiment 1;
Fig. 2 is the prepared manganese dioxide/sem photograph of graphene oxide combination electrode material under high-amplification-factor of embodiment 1;
Fig. 3 is the cycle performance figure that the lithium battery of the prepared manganese dioxide/graphene oxide combination electrode material of embodiment 1 discharges and recharges under the 0.1C condition.
Embodiment
Embodiment describes in further detail the present invention below in conjunction with accompanying drawing.
Embodiment 1
The preparation of manganese dioxide/stannic oxide/graphene nano combination electrode material: with manganese sulfate, ammonium persulfate and graphene oxide as raw material; The mol ratio of control manganese sulfate and ammonium persulfate is 1: 1; Graphene oxide adds by 10% of theoretical product manganese dioxide weight; In water, evenly mixed 1 hour, place autoclave to react 24 hours down, obtain lithium battery with manganese dioxide/stannic oxide/graphene nano combination electrode material in 90 degree.Fig. 1 and 2 is the sem photograph of combination electrode material.
The making of lithium secondary battery: active material manganese dioxide/stannic oxide/graphene nano combination electrode material, conductive agent Super P and binding agent vinylidene in n-formyl sarcolysine base pyrrolidones are mixed by mass ratio at 85: 10: 5; And be coated on the aluminium foil, 80 ℃ of following dryings obtain electrode slice.Be negative pole with the lithium sheet subsequently, microporous polypropylene film is a barrier film, the LiPF of 1mol/L
4Non-aqueous solution (solvent is the mixed solvent of isopyknic dimethyl carbonate and dipropyl carbonate) is an electrolyte, and electrode pad set is dressed up the button cell test performance therewith.
Button cell performance test: under 25 ℃ of conditions, battery is carried out the constant current charge-discharge test in the 1.5V-4.5V voltage range.Fig. 3 is the cycle performance figure that the lithium secondary battery of prepared manganese dioxide/graphene oxide combination electrode material discharges and recharges under the 0.1C condition, can find out that the battery specific capacity is about 170mAh/g, and cycle performance is very excellent, and 40 times the circulation back does not have obviously decay.
Embodiment 2
Manganese dioxide/stannic oxide/graphene nano combination electrode material preparation is identical with embodiment 1, with the electrode active material of this material as lithium battery, and the assembling button cell.The making of lithium secondary battery and embodiment 1 are basic identical; Difference is to adopt this material as negative electrode active material; With mix in conductive agent Super P and the binding agent vinylidene n-formyl sarcolysine base pyrrolidones after coat on the Copper Foil, 80 ℃ are down dry, with this negative plate as battery.In the 0.1V-2V voltage range, be 1534mAh/g through constant current charge-discharge test shows battery reversible specific capacity, 50 capacity of circulation can remain on more than the 950mAh/g under 0.1C.
Embodiment 3
By weight being in the aqueous solution fully to mix at 90: 10, hybrid mode is that machinery stirred 1 hour earlier with manganese dioxide and Graphene, and ultrasonic then 30 minutes, spray-dried granulation obtained lithium battery with manganese dioxide/graphene nano combination electrode material.With the electrode active material of this material as lithium battery; The assembling button cell, the making of lithium secondary battery is identical with embodiment 1, in the 1.5V-4.5V voltage range; Through constant current charge-discharge test shows battery specific capacity is 180mAh/g, 100 decay 2% of circulation under 0.1C.
Embodiment 4
With ammonium metavanadate, PEG400 and graphene oxide as raw material; Graphene oxide adds by 15% of theoretical product vanadic oxide weight, in water, evenly mixes 1 hour, regulates pH value between 3.5-5.5 through rare nitric acid; Place autoclave to react 24 hours down in 180 degree; Obtain lithium battery with vanadic oxide/stannic oxide/graphene nano combination electrode material, with the electrode active material of this material as lithium battery, the assembling button cell; The making of lithium secondary battery is identical with embodiment 1; In the 1.5V-3.5V voltage range, be 408mAh/g through constant current charge-discharge test shows battery reversible specific capacity, each circulation volume decay is below 0.15% under 0.1C.
By weight being through mechanical agitation fully to mix at 95: 5, spray-dried granulation obtains lithium battery with vanadic oxide/graphene nano combination electrode material with vanadic oxide colloidal sol and Graphene.With the electrode active material of this material as lithium battery; The assembling button cell; The making of lithium secondary battery is identical with embodiment 1; In the 1.5V-3.5V voltage range, be 417mAh/g through constant current charge-discharge test shows battery reversible specific capacity, each circulation volume decay is below 0.1% under 0.1C.
Embodiment 6
Adopt ferrous sulfate, hydrogen peroxide and Graphene as raw material, the three was evenly mixed 1 hour in water in proportion, Graphene adds by 5% of theoretical product FeOOH weight; Place autoclave to react 24 hours down in 150 degree; Obtain lithium battery with FeOOH/graphene nano combination electrode material, with the electrode active material of this material as lithium battery, the assembling button cell; The making of lithium secondary battery is identical with embodiment 1; In the 1.5V-4V voltage range, be 268mAh/g through constant current charge-discharge test shows battery reversible specific capacity, 50 capacity of circulation do not have obvious decay under the 0.1C condition.
Embodiment 7
By weight being through mechanical agitation fully to mix at 95: 5, spray-dried granulation obtains lithium battery with FeOOH/graphene nano combination electrode material with FeOOH and Graphene.With the electrode active material of this material as lithium battery; The assembling button cell, the making of lithium secondary battery is identical with embodiment 1, in the 1.5V-4V voltage range; Through constant current charge-discharge test shows battery reversible specific capacity is 274mAh/g, and 100 capacity attenuations of circulation are below 2% under 0.1C.
Embodiment 8
Adopt chromium trioxide and Graphene as raw material, both persons were evenly mixed 1 hour in water in proportion, Graphene adds by 8% of theoretical product chrome green weight; Place autoclave to react 1 hour down in 190 degree; Obtain lithium battery with chrome green/graphene nano combination electrode material, with the electrode active material of this material as lithium battery, the assembling button cell; The making of lithium secondary battery is identical with embodiment 1; In the 2V-4.2V voltage range, be 247mAh/g through constant current charge-discharge test shows battery reversible specific capacity, 100 capacity attenuations 3% of circulation under the 0.1C condition.
Embodiment 9
The preparation of chrome green/graphene nano combination electrode material is identical with embodiment 8, with the electrode active material of this material as lithium battery, and the assembling button cell.The making of lithium secondary battery and embodiment 1 are basic identical; Difference is to adopt this material as negative electrode active material; With mix in conductive agent Super P and the binding agent vinylidene n-formyl sarcolysine base pyrrolidones after coat on the Copper Foil, 80 ℃ are down dry, with this negative plate as battery.In the 0.1V-1.5V voltage range, be 814mAh/g through constant current charge-discharge test shows battery reversible specific capacity, 50 capacity attenuations of circulation are below 5% under 0.1C.
By weight being through mechanical agitation fully to mix at 90: 10, spray-dried granulation obtains lithium battery with five oxidations, two chromium/graphene nano combination electrode material with five oxidations, two chromium and Graphene.With the electrode active material of this material as lithium battery; The assembling button cell, the making of lithium secondary battery is identical with embodiment 1, in the 2V-4.2V voltage range; Through constant current charge-discharge test shows battery reversible specific capacity is 256mAh/g, and each circulation volume decay is below 0.1% under 0.1C.
Embodiment 11
With ammonium heptamolybdate and graphene oxide as raw material; Graphene oxide adds by 10% of theoretical product molybdenum trioxide weight, in water, evenly mixes 1 hour, regulates pH value to 1 through nitric acid; Place autoclave to react 30 hours down in 180 degree; Obtain lithium battery with molybdenum trioxide/stannic oxide/graphene nano combination electrode material, with the electrode active material of this material as lithium battery, the assembling button cell.The making of lithium secondary battery and embodiment 1 are basic identical; Difference is to adopt this material as negative electrode active material; With mix in conductive agent Super P and the binding agent vinylidene n-formyl sarcolysine base pyrrolidones after coat on the Copper Foil, 80 ℃ are down dry, with this negative plate as battery.In the 0.1V-1.5V voltage range, be 1246mAh/g through constant current charge-discharge test shows battery reversible specific capacity, 50 capacity of circulation can remain on more than the 1000mAh/g under 0.1C.
Embodiment 12
By weight being through mechanical agitation fully to mix at 95: 5, spray-dried granulation obtains lithium battery with molybdenum trioxide/graphene nano combination electrode material with molybdenum trioxide colloidal sol and Graphene.With the electrode active material of this material as lithium battery; The assembling button cell; The making of lithium secondary battery is identical with embodiment 1; In the 1.5V-3.2V voltage range, be 353mAh/g through constant current charge-discharge test shows battery reversible specific capacity, 50 capacity of circulation can remain on more than the 300mAh/g under 0.1C.
Embodiment 13
With manganese sulfate, ferric nitrate, ethanedioic acid, ammonium persulfate and graphene oxide as raw material; The mol ratio of control manganese sulfate and ferric nitrate is 10: 1, and graphene oxide adds by 10% of theoretical product ferromanganese oxide weight, in water, evenly mixes 1 hour; Place autoclave to react 40 hours down in 180 degree; Obtain lithium battery with ferromanganese oxide/stannic oxide/graphene nano combination electrode material, with the electrode active material of this material as lithium battery, the assembling button cell.The making of lithium secondary battery is identical with embodiment 1, in the 1.5V-4V voltage range, is 213mAh/g through constant current charge-discharge test shows battery reversible specific capacity, and 40 capacity of circulation do not have obvious decay under the 0.1C condition.
Claims (10)
1. a lithium battery is with transition metal oxide/graphene nano combination electrode material; It is characterized in that this lithium battery uses the transition metal oxide of transition metal oxide/graphene nano combination electrode material as Graphene or graphene oxide modification; Said Graphene or graphene oxide are connected with the mode of transition metal oxide through physics parcel or chemical bonding, and wherein the mass ratio of Graphene or graphene oxide and transition metal oxide is 0.01: 100～50: 100.
2. lithium battery according to claim 1 is with transition metal oxide/graphene nano combination electrode material; It is characterized in that said transition metal oxide is the oxide of manganese, comprise manganese dioxide, manganese sesquioxide managnic oxide, mangano-manganic oxide or the embedding lithium manganese oxide of different crystal forms; The oxide of vanadium comprises α phase, amorphous vanadic oxide or embedding lithium-barium oxide; The oxide of iron comprises FeOOH, magnetic iron ore tri-iron tetroxide or bloodstone α-di-iron trioxide; The oxide of chromium comprises chrome green, chromium dioxide, five oxidations, two chromium, 15 oxidations, six chromium or eight oxidations, three chromium; The oxide of molybdenum comprises molybdenum trioxide, 11 oxidations, four molybdenums, 23 oxidations, eight molybdenums or 26 oxidations, nine molybdenums; Perhaps some other transition metal oxide and embedding lithium oxide thereof.
3. lithium battery according to claim 1 is with transition metal oxide/graphene nano combination electrode material; It is characterized in that said Graphene is individual layer or is made up of the two-dimentional lonsdaleite material of the number of plies between one to three layer that graphene oxide is to contain hydroxyl or carboxyl or epoxy radicals on the Graphene.
4. lithium battery according to claim 1 is characterized in that with transition metal oxide/graphene nano combination electrode material said lithium battery is used as positive electrode active materials or negative active core-shell material with transition metal oxide/graphene nano combination electrode material in lithium battery.
5. a lithium battery is with the preparation method of transition metal oxide/graphene nano combination electrode material; It is characterized in that step is: the precursor that Graphene or graphene oxide and preparation transition metal oxide is required is in solvent, evenly to mix in 0.01: 100～50: 100 by mass ratio; Place autoclave; Reaction is more than 1 hour under 60～300 ℃ of conditions, and the lithium battery that obtains chemical bonding is with transition metal oxide/graphene nano combination electrode material; Be in solvent, fully to mix in 0.01: 100～50: 100 by mass ratio perhaps with Graphene or graphene oxide and transition metal oxide, through the dry lithium battery that obtains the physics parcel with transition metal oxide/graphene nano combination electrode material.
6. preparation method according to claim 5 is characterized in that the required precursor of said preparation transition metal oxide is meant required slaine and oxidant or the reducing agent of preparation transition metal oxide.
7. preparation method according to claim 5 is characterized in that said transition metal oxide is the oxide of manganese, comprises manganese dioxide, manganese sesquioxide managnic oxide, mangano-manganic oxide or the embedding lithium manganese oxide of different crystal forms; The oxide of vanadium comprises α phase, amorphous vanadic oxide or embedding lithium-barium oxide; The oxide of iron comprises FeOOH, magnetic iron ore tri-iron tetroxide or bloodstone α-di-iron trioxide; The oxide of chromium comprises chrome green, chromium dioxide, five oxidations, two chromium, 15 oxidations, six chromium or eight oxidations, three chromium; The oxide of molybdenum comprises molybdenum trioxide, 11 oxidations, four molybdenums, 23 oxidations, eight molybdenums or 26 oxidations, nine molybdenums; Perhaps some other transition metal oxide and embedding lithium oxide thereof.
8. preparation method according to claim 5 is characterized in that said mixed media is mechanical agitation, ball milling, the one or more combination in ultrasonic, and incorporation time is 0.5-30 hour.
9. preparation method according to claim 5 is characterized in that said solvent is water, ethanol, acetone, dimethyl sulfoxide (DMSO), N, dinethylformamide, oxolane, chloroform, carbon tetrachloride or dichloro-benzenes.
10. preparation method according to claim 5 is characterized in that said dry means are spray drying or direct drying.
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