CN107492652A - Cathode of lithium battery zwitterion codope tin-based oxide and preparation method thereof - Google Patents

Cathode of lithium battery zwitterion codope tin-based oxide and preparation method thereof Download PDF

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Publication number
CN107492652A
CN107492652A CN201710555566.4A CN201710555566A CN107492652A CN 107492652 A CN107492652 A CN 107492652A CN 201710555566 A CN201710555566 A CN 201710555566A CN 107492652 A CN107492652 A CN 107492652A
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cathode
zwitterion
lithium battery
sno
tin
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万宁
杨茂萍
郭钰静
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Hefei Gotion High Tech Power Energy Co Ltd
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Hefei Guoxuan High Tech Power Energy Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The invention discloses a kind of preparation method of cathode of lithium battery zwitterion codope tin-based oxide to comprise the following steps：Pink salt and molysite are subjected to one step hydro thermal method and prepare Fe/SnO2Nano composite material；By Fe/SnO2Nano composite material is placed in sintering in nitrogen atmosphere or ammonia atmosphere and obtains cathode of lithium battery zwitterion codope tin-based oxide.The invention also discloses a kind of cathode of lithium battery zwitterion codope tin-based oxide.The present invention uses ferro element and nitrogen codope SnO2, so as to have the function that more preferable volume buffering effect and improve electronic conductivity, electrode material is more beneficial for Li+Insertion and abjection.The lithium capacity embedding first of the present invention is 1960mAh/g, and specific capacity may remain in 680mAh/g after 50 repeated charge-discharge cycles.Preparation method technique provided by the invention is simple, environment-friendly, it is easy to accomplish industrialized production.

Description

Cathode of lithium battery zwitterion codope tin-based oxide and preparation method thereof
Technical field
The present invention relates to technical field of lithium ion, more particularly to a kind of cathode of lithium battery zwitterion codope tin Base oxide and preparation method thereof.
Background technology
With the development of modern science and technology, high-performance lithium ion battery is in domestic electronic appliances, electric car and large-scale solid Determine to play the part of important role in battery.As expected, obtain lithium ion battery by way of improving chemical property The demand of get Geng Gao energy density, longer cycle life and more preferable security increasingly rises.Because they focus in fact Border apply and safety problem, energy density and cycle life, so focus more in recent years battery research, and by these because Element is considered among follow-on high performance lithium ion battery.Nowadays, carbon graphite is commonly used as commercial Li-ion batteries negative pole Material.But the current potential of the electrode potential and lithium due to carbon is very close to when the battery is overcharged, having part lithium ion in carbon Electrode surface deposits, and forms Li dendrite and triggers safety issue.When on the other hand, due to carbon graphite first time discharge and recharge, meeting Solid-electrolyte interphace (Solid Electrolyte Interface Film, abbreviation SEI film) is formed in carbon surface, is caused Larger irreversible capacity loss, and the generation of SEI films adds electrode/electrolyte interface impedance, is unfavorable for Li+It is reversible Embedded and abjection.Compared to the negative material of more other candidates, the obvious deficiency of carbon graphite is that capacity is low (with crystal/unformed silicon Compare), high rate performance is poor (with spinelle Li4Ti5O12Compare), and to lack other not available good performances excellent Gesture.Searching security performance is more preferable, the novel anode material that specific capacity is higher, cycle life is longer, it has also become lithium ion battery is ground The focus studied carefully.
According to all kinds of reports, metal oxide negative material is proved with good performance afterwards by effectively modified. Especially SnO2, its first phase transformation reaction can discharge 1494mAh/g by Li-Sn alloying reactions；The lithium of theoretical specific capacity is deposited Storage mechanism is widely studied Although SnO2Theoretical specific capacity be four times of carbon graphite, but it is that capacity retention is poor that its electrode material is clearly disadvantageous, warp Its rear capacity that is circulated throughout crossed repeatedly has obvious decay.The decay of this capacity is mainly due to the insertion/de- in lithium ion During going out stereomutation reach 250% and caused by electrode material efflorescence.By prolonged circulation, SnO2Electrode material Efflorescence directly contribute the rapid decay of its capacity, and uncontrolled Volume Changes result in the rupture of its electrode, these It will result directly in collector and electronic conduction net loose contact.This stereomutation will cause SnO2The SEI films of electrode surface Increase, thus make its corresponding electrochemical mechanism unstable.More importantly poor capacity keeps inevitably circulating During capacity is decayed rapidly, especially at higher current densities.Therefore, by suppressing the efflorescence and stereomutation of material, The further electron conduction that improves makes SnO2The capacity retention of electrode can be improved, and be further applied to lithium from It is necessary among sub- battery.
One kind improves SnO2The effective ways of electrode electro Chemical performance are the changes for suppressing its volume with improving electrode material Electronic conductivity, make the significantly more efficient insertion/abjection of lithium ion.In order to reach this purpose, by element doping to SnO2It is brilliant It is a kind of effective method in lattice.Recently, metallic element is successfully doped to SnO2In lattice, and study discovery doping Sample afterwards has the function that volume buffering and electron conduction improve.On the other hand, it has already been proven that N doping SnO2Show Superior electrical and optical performance, and may preferably improve electronic conductivity.Therefore, metallic element and nitrogen codope SnO2Sample should make full use of its effect for increasing the buffering effect of volume and improving electronic conductivity, make SnO2Electrode more has Beneficial to Li+Reversible insertion and abjection.However, metallic element and nitrogen codope SnO2The chemical property of sample there is not yet Report.
The content of the invention
Based on technical problem existing for background technology, the present invention proposes a kind of cathode of lithium battery zwitterion codope The collaboration chanza of tin-based oxide and preparation method thereof, iron and nitrogen, makes SnO2Electronics and ionic conductivity obtain Improve, reduce the irreversible capacity loss in first week, and because the doping of iron and nitrogen has relaxed SnO2Electrode material exists The bulking effect of volume, further improves SnO in cyclic process2Cyclical stability, while add crystallization the degree of order, Specific surface area, aperture and electrical conductivity, so as to promote the diffusion of lithium ion, and then the high rate performance of electrode material can be improved； And preparation method is simple, get a good chance of turning into the commercialized lithium ion battery negative material of a new generation.
A kind of preparation method of cathode of lithium battery zwitterion codope tin-based oxide proposed by the present invention, including such as Lower step：
S1, pink salt and molysite are carried out to one step hydro thermal method preparation Fe/SnO2Nano composite material；
S2, by Fe/SnO2Nano composite material is placed in sintering in nitrogen atmosphere or ammonia atmosphere and obtains cathode of lithium battery use Zwitterion codope tin-based oxide.
Preferably, S1 concrete operations are as follows：Solution A is obtained by pink salt and molysite are soluble in water；Sodium hydroxide is dissolved in Solution B is obtained in water；Solution A is added dropwise in solution B and obtains solution C；Solution C is subjected to hydro-thermal reaction, centrifuged, washing obtains Fe/SnO2Nano composite material.
Preferably, in S1, pink salt be butter of tin, stannous chloride, stannous sulfate, sodium stannate, it is a kind of in sodium stannite or Two or more compositions.
Preferably, in S1, molysite is one in frerrous chloride, ferrous sulfate, ferrous nitrate, iron chloride, ferric sulfate, ferric nitrate Kind or two or more compositions.
Preferably, in S1, the mol ratio of tin element, ferro element and sodium hydroxide is 1：60：7；The mol ratio is theoretical value, Derived by final product, but excessive pink salt, molysite and/or sodium hydroxide are often added in actual production process, made The ratio of three is not 1：60：7, finished with promoting pink salt, molysite or sodium hydroxide to react as far as possible.
Preferably, in S1, solution A is added dropwise in solution B and obtains solution C, rate of addition is 15-20 drops/min, is added dropwise During persistently stir.
Preferably, in S1, solution C and the volume ratio of hydrothermal reaction kettle internal volume are 2-3：4.
Preferably, in S1, the temperature of hydro-thermal reaction is 180-200 DEG C, and the time of hydro-thermal reaction is 12-24h.
Preferably, in S1, centrifugal rotational speed 3500-4500r/min.
Preferably, in S1, washed respectively using ethanol and deionized water.
Preferably, in S2, sintering temperature is 450-550 DEG C, sintering time 8-12h.
The present invention also proposes a kind of cathode of lithium battery zwitterion codope tin-based oxide, is born using above-mentioned lithium battery Pole is made with the preparation method of zwitterion codope tin-based oxide.
Preferably, there is hierarchy, its grain diameter is 30-40nm.
The present invention is combined into the electrode material of advantageous lithium ion battery using the design and coordination of material structure, and And its preparation technology is simple, it is easy to accomplish large-scale production.
Cation doping SnO is prepared using hydro-thermal reaction in the present invention2Nano particle (i.e. Fe/SnO2Nano combined material Material), and cathode of lithium battery zwitterion codope tinbase is prepared after further sintering under nitrogen or ammonia atmosphere Oxide.Storage lithium performance test shows that reversible capacity when the electrode obtained material of the present invention circulates between 0.005-3.0V is remote Higher than SnO2And Fe/SnO2The reversible capacity of electrode material, the charging curve of three also have significant difference, and this may be attributed to iron With the synergy of nitrogen, make SnO2Electronics and ionic conductivity be improved, reduce the irreversible capacity damage in first week Lose, simultaneously because the doping of iron and nitrogen has relaxed SnO2The bulking effect of electrode material volume in cyclic process, enters one Step improves SnO2Cyclical stability.
Gained cathode of lithium battery of the invention with zwitterion codope tin-based oxide due to less particle size, one Determine to have relaxed the change of material volume in cyclic process in degree, can preferably improve cycle performance；Secondly, present invention side Method adds the crystallization degree of order, specific surface area, aperture and electrical conductivity, so as to promote the diffusion of lithium ion, and then can carry The high rate performance of high electrode material.
Sum it up, present invention gained cathode of lithium battery demonstrates what is had with zwitterion codope tin-based oxide Cycle performance and high rate performance.With original SnO2Material is compared, cathode of lithium battery zwitterion codope tin-based oxide The chemical property of material is substantially improved, and it is easily prepared, get a good chance of turning into the commercialized lithium ion battery of a new generation Negative material.
Embedding lithium capacity is reachable first with zwitterion codope tin-based oxide for gained cathode of lithium battery of the invention 1960mAh/g, reversible de- lithium capacity is up to 1167mAh/g, and initial coulomb efficiency is up to 60%, and specific capacity is in 50 charge and discharges repeatedly Still up to 645mAh/g after electricity circulation.
Brief description of the drawings
Fig. 1 is the gained cathode of lithium battery zwitterion codope tin-based oxide of embodiment 8 and Fe/SnO2It is nano combined Material, pure phase SnO2X-ray diffractogram.
Fig. 2 is the gained cathode of lithium battery zwitterion codope tin-based oxide of embodiment 8 and Fe/SnO2It is nano combined Material, pure phase SnO2FESEM figure；Wherein Fig. 2 a1 and Fig. 2 a2 are pure phase SnO2FESEM figure, Fig. 2 b1 and Fig. 2 b2 for implement The gained Fe/SnO of example 82The FESEM figures of nano composite material, Fig. 2 c1 and Fig. 2 c2 are the gained cathode of lithium battery negative and positive of embodiment 8 The FESEM figures of ion codope tin-based oxide.
Fig. 3 is the gained cathode of lithium battery zwitterion codope tin-based oxide of embodiment 8 and Fe/SnO2It is nano combined Material, pure phase SnO2HRTEM figure with SAED scheme；Wherein Fig. 3 a are pure phase SnO2HRTEM figure with SAED scheme, Fig. 3 b for implement The gained Fe/SnO of example 82HRTEM figures and the SAED of nano composite material scheme, and Fig. 3 c are the gained cathode of lithium battery negative and positive of embodiment 8 HRTEM figures and the SAED of ion codope tin-based oxide scheme, and Fig. 3 d are rutile SnO2Lattice structure model (2D).
Fig. 4 is respectively with the gained cathode of lithium battery zwitterion codope tin-based oxide of embodiment 8, Fe/SnO2Receive Nano composite material and pure phase SnO2Negative electrode is in the head weeks that voltage is 0.005-3V, current density is 0.1C obtained by active material Charging and discharging curve.
Fig. 5 is respectively with the gained cathode of lithium battery zwitterion codope tin-based oxide of embodiment 8, Fe/SnO2Receive Nano composite material and pure phase SnO2Negative electrode is in current density 0.1C cycle characteristics figures obtained by active material.
Fig. 6 is respectively with the gained cathode of lithium battery zwitterion codope tin-based oxide of embodiment 8, Fe/SnO2Receive Nano composite material and pure phase SnO2Negative electrode carries out the test chart of high rate performance after circulation in 50 weeks obtained by active material.
In above-mentioned figure, Pure SnO2For pure phase SnO2, Fe/SnO2For the gained Fe/SnO of the embodiment of the present invention 82It is nano combined Material, Fe-N/SnO2For the gained cathode of lithium battery zwitterion codope tin-based oxide of the embodiment of the present invention 8, Dis is represented Discharge (Discharge), Cha represents charging (Charge).
Embodiment
Below, technical scheme is described in detail by specific embodiment.
Embodiment 1
A kind of preparation method of cathode of lithium battery zwitterion codope tin-based oxide proposed by the present invention, including such as Lower step：
S1, pink salt and molysite are carried out to one step hydro thermal method preparation Fe/SnO2Nano composite material；
S2, by Fe/SnO2Nano composite material is placed in sintering in nitrogen atmosphere or ammonia atmosphere and obtains cathode of lithium battery use Zwitterion codope tin-based oxide.
Embodiment 2
A kind of preparation method of cathode of lithium battery zwitterion codope tin-based oxide proposed by the present invention, including such as Lower step：
S1, obtain solution A by butter of tin and ferric nitrate are soluble in water；Solution B is obtained by sodium hydroxide is soluble in water；Tin The mol ratio of ion, iron ion and sodium hydroxide is 1：60：7；Solution A is added dropwise in solution B and obtains solution C, rate of addition For 15-20 drops/min, persistently stirred during dropwise addition；Solution C is subjected to hydro-thermal reaction, the temperature of hydro-thermal reaction is 180 DEG C, water The time of thermal response is 24h, centrifugation, centrifugal rotational speed 3500r/min, is washed to obtain respectively using ethanol and deionized water Fe/SnO2Nano composite material；
S2, by Fe/SnO2Nano composite material is placed in nitrogen atmosphere or ammonia atmosphere and sintered, and sintering temperature is 450 DEG C, Sintering time is that 12h obtains cathode of lithium battery zwitterion codope tin-based oxide.
Embodiment 3
A kind of preparation method of cathode of lithium battery zwitterion codope tin-based oxide proposed by the present invention, including such as Lower step：
S1, obtain solution A by butter of tin and ferric nitrate are soluble in water；Solution B is obtained by sodium hydroxide is soluble in water；Tin The mol ratio of ion, iron ion and sodium hydroxide is 1：60：7；Solution A is added dropwise in solution B and obtains solution C, rate of addition For 15-20 drops/min, persistently stirred during dropwise addition；Solution C is subjected to hydro-thermal reaction, the temperature of hydro-thermal reaction is 200 DEG C, water The time of thermal response is 12h, centrifugation, centrifugal rotational speed 4500r/min, is washed to obtain respectively using ethanol and deionized water Fe/SnO2Nano composite material；
S2, by Fe/SnO2Nano composite material is placed in nitrogen atmosphere or ammonia atmosphere and sintered, and sintering temperature is 550 DEG C, Sintering time is that 8h obtains cathode of lithium battery zwitterion codope tin-based oxide.
Embodiment 4
A kind of preparation method of cathode of lithium battery zwitterion codope tin-based oxide proposed by the present invention, including such as Lower step：
S1, by 2.80gSnCl4·5H2O and 0.48mmolFe (NO3)3·9H2O is dissolved in 40mL deionized waters, is stirred To clear solution A (mixing speed 700r/min)；2.24g NaOH are dissolved in 40mL deionized waters, stirring obtains transparent molten Liquid B (mixing speed 700r/min)；Solution A is slowly dropped in solution B, drop speed is 15-20 drops/min, during dropwise addition Lasting stirring, mixing speed 720r/min, obtains clear solution C；Clear solution C is placed in reactor, the water at 180 DEG C Sediment is obtained after thermal response 24h, is centrifuged, with deionized water and absolute ethyl alcohol washing precipitate repeatedly, is obtained after 70 DEG C of drying Fe/SnO2Nano composite material；
S2, by Fe/SnO2500 DEG C of annealing 10h obtain cathode of lithium battery negative and positive to nano composite material under nitrogen atmosphere Ion codope tin-based oxide.
Embodiment 5
A kind of preparation method of cathode of lithium battery zwitterion codope tin-based oxide proposed by the present invention, including such as Lower step：
S1, by 1.40gSnCl4·5H2O and 0.24mmolFe (NO3)3·9H2O is dissolved in 20mL deionized waters, is stirred To clear solution A (mixing speed 700r/min)；1.12g NaOH are dissolved in 20mL deionized waters, stirring obtains transparent molten Liquid B (mixing speed 700r/min)；Solution A is slowly dropped in solution B, drop speed is 15-20 drops/min, during dropwise addition Lasting stirring, mixing speed 720r/min, obtains clear solution C；Clear solution C is placed in reactor, the water at 180 DEG C Sediment is obtained after thermal response 16h, is centrifuged, with deionized water and absolute ethyl alcohol washing precipitate repeatedly, is obtained after 70 DEG C of drying Fe/SnO2Nano composite material；
S2, by Fe/SnO2500 DEG C of annealing 10h obtain cathode of lithium battery negative and positive to nano composite material under nitrogen atmosphere Ion codope tin-based oxide.
Embodiment 6
A kind of preparation method of cathode of lithium battery zwitterion codope tin-based oxide proposed by the present invention, including such as Lower step：
S1, by 1.40gSnCl4·5H2O and 0.24mmolFe (NO3)3·9H2O is dissolved in 20mL deionized waters, is stirred To clear solution A (mixing speed 700r/min)；1.12g NaOH are dissolved in 20mL deionized waters, stirring obtains transparent molten Liquid B (mixing speed 700r/min)；Solution A is slowly dropped in solution B, drop speed is 15-20 drops/min, during dropwise addition Lasting stirring, mixing speed 720r/min, obtains clear solution C；Clear solution C is placed in reactor, the water at 180 DEG C Sediment is obtained after thermal response 12h, is centrifuged, with deionized water and absolute ethyl alcohol washing precipitate repeatedly, is obtained after 70 DEG C of drying Fe/SnO2Nano composite material；
S2, by Fe/SnO2450 DEG C of annealing 12h obtain cathode of lithium battery negative and positive to nano composite material under nitrogen atmosphere Ion codope tin-based oxide.
Embodiment 7
A kind of preparation method of cathode of lithium battery zwitterion codope tin-based oxide proposed by the present invention, including such as Lower step：
S1, by 2.80gSnCl4·5H2O and 0.48mmolFe (NO3)3·9H2O is dissolved in 40mL deionized waters, is stirred To clear solution A (mixing speed 700r/min)；2.24g NaOH are dissolved in 40mL deionized waters, stirring obtains transparent molten Liquid B (mixing speed 700r/min)；Solution A is slowly dropped in solution B, drop speed is 15-20 drops/min, during dropwise addition Lasting stirring, mixing speed 720r/min, obtains clear solution C；Clear solution C is placed in reactor, the water at 180 DEG C Sediment is obtained after thermal response 24h, is centrifuged, with deionized water and absolute ethyl alcohol washing precipitate repeatedly, is obtained after 70 DEG C of drying Fe/SnO2Nano composite material；
S2, by Fe/SnO2Nano composite material under nitrogen atmosphere 550 DEG C annealing 8h obtain cathode of lithium battery negative and positive from Sub- codope tin-based oxide.
Embodiment 8
A kind of preparation method of cathode of lithium battery zwitterion codope tin-based oxide proposed by the present invention, including such as Lower step：
S1, by 1.40gSnCl4·5H2O and 0.24mmolFe (NO3)3·9H2O is dissolved in 20mL deionized waters, is stirred To clear solution A (mixing speed 700r/min)；1.12g NaOH are dissolved in 20mL deionized waters, stirring obtains transparent molten Liquid B (mixing speed 700r/min)；Solution A is slowly dropped in solution B, drop speed is 15-20 drops/min, during dropwise addition Lasting stirring, mixing speed 720r/min, obtains clear solution C；Clear solution C is placed in reactor, the water at 180 DEG C Sediment is obtained after thermal response 12h, is centrifuged, with deionized water and absolute ethyl alcohol washing precipitate repeatedly, is obtained after 70 DEG C of drying Fe/SnO2Nano composite material；
S2, by Fe/SnO2500 DEG C of annealing 12h obtain cathode of lithium battery negative and positive to nano composite material under nitrogen atmosphere Ion codope tin-based oxide.
The gained cathode of lithium battery of embodiment 8 is tested with zwitterion codope tin-based oxide, its result is as follows：
1st, X-ray diffraction is carried out to it, as shown in figure 1, Fig. 1 is that the gained cathode of lithium battery zwitterion of embodiment 8 is double Adulterate tin-based oxide and Fe/SnO2Nano composite material, pure phase SnO2X-ray diffractogram；As shown in Figure 1：The institute of embodiment 8 Cathode of lithium battery it is relatively good with the crystallinity of zwitterion codope tin-based oxide, cathode of lithium battery zwitterion is double-doped Miscellaneous tin-based oxide and Fe/SnO2Nano composite material, pure phase SnO2It is cubic phase rutile SnO2(JCPDS card numbers：01- 0657) diffraction maximum for not having impurity after, that is, adulterating occurs, and illustrates that doping does not change SnO2Phase structure；
2nd, field emission scanning electron microscope scanning is carried out to it, born as shown in Fig. 2 Fig. 2 is the gained lithium battery of embodiment 8 Pole zwitterion codope tin-based oxide and Fe/SnO2Nano composite material, pure phase SnO2FESEM figure；As shown in Figure 2： Three kinds of materials are less than 100nm nano SnO by size2Particle forms；Wherein pure phase SnO2It is that an average-size is 500nm Hierarchy spheroid, by the length of side be 80nm nanocube form；And ferro element doping and iron, nitrogen codope it Afterwards, hence it is evident that change SnO2Pattern, in Fig. 2 b1, Fig. 2 b2, Fig. 2 c1 and Fig. 2 c2, Fe/SnO2 nano composite materials and lithium GND with zwitterion codope tin-based oxide is formed by 30-40nm nanoparticle agglomerates, compared to pure phase SnO2Primary particle size (80nm) it is much smaller；The particle size of sample effectively will shorten lithium ion in charge and discharge after modification Diffusion length in electric process, and the speed of discharge and recharge is accelerated, therefore smaller size of particle is more beneficial for discharging SnO2 Internal pressure, and effectively relaxed the change of volume during removal lithium embedded；
3rd, high-resolution transmission electron microscope transmission is carried out to it, as shown in figure 3, Fig. 3 is the gained cathode of lithium battery of embodiment 8 With zwitterion codope tin-based oxide and Fe/SnO2Nano composite material, pure phase SnO2HRTEM figure with constituency SAED scheme； As shown in Figure 3：SnO2Crystal grain shows similar particle size and clear regular lattice fringe；In Fig. 3 a, Fig. 3 b, Fig. 3 c In, show that one is uniform, clearly d spacing is 0.335nm, 0.337nm and 0.338nm (110) on (001) crystal zone axis Lattice fringe；And Fig. 3 d are rutile SnO2Lattice structure model (2D), clearly show that out (110) interplanar distance；I.e. without it Its crystal face or d spacing illustrates：The gained cathode of lithium battery of embodiment 8 is with zwitterion codope tin-based oxide without dephasign In the presence of；Proved by the way that the SAED figures in the upper right corner are further, the SnO of pure phase/doping2Corresponding electron diffraction spot exists [001] on * crystal zone axis, it can be seen that the SnO after iron and nitrogen codope2Difference is had no with the rutile SnO2 of pure phase, and And the appearance of dephasign is not found in all particle surfaces, this has confirmed Fig. 1 XRD results well.
Prepare negative electrode：Respectively by the gained cathode of lithium battery of embodiment 8 zwitterion codope tin-based oxide, Fe/ SnO2Nano composite material, pure phase SnO2It is 7 in mass ratio by active material and acetylene black, bonding agent as active material：2：1 Mixing, grinding is uniform, adds appropriate 1-Methyl-2-Pyrrolidone and slurry is made, slurry is equably coated on copper foil, infrared After lamp drying, 120 DEG C of vacuum drying 24h, 8mm × 8mm electrode slice is then determined, claims its quality with electronic analytical balance, and Calculate the quality of active material.
Electrode performance is tested：Performance test is carried out in fastening lithium ionic cell；Battery assembling mode is as follows：Made with lithium piece For to electrode, Celgard2300 as barrier film, electrolyte use concentration for 1mol/L lithium hexafluoro phosphate ethylene carbonate- Methyl ethyl ester (1：1) solution.During test, temperature is room temperature, using constant current charge-discharge, current density 76.6mA/g, Control reference voltage is 0.005-3.0V.
As shown in Figure 4, Figure 5 and Figure 6, Fig. 4 is respectively with the gained cathode of lithium battery of embodiment 8 use to electrode performance test result Zwitterion codope tin-based oxide, Fe/SnO2Nano composite material and pure phase SnO2Negative electrode is in electricity obtained by active material Press the first all charging and discharging curves for being 0.1C for 0.005-3V, current density.Fig. 5 is respectively with the gained cathode of lithium battery of embodiment 8 With zwitterion codope tin-based oxide, Fe/SnO2Nano composite material and pure phase SnO2The negative electrode obtained by active material exists Voltage is 0.005-3V, current density is 0.1C cycle characteristics figures.Fig. 6 is cloudy with the gained cathode of lithium battery of embodiment 8 respectively Cation codope tin-based oxide, Fe/SnO2Nano composite material and pure phase SnO2Negative electrode was through 50 weeks obtained by active material The test chart of high rate performance is carried out after circulation.
As shown in Figure 4：Nitrogen-doping adds Fe/SnO2The charge/discharge capacity in nano composite material first week, this may It is attributed to and improves crystallinity and electrical conductivity.The gained cathode of lithium battery of embodiment 8 is aoxidized with zwitterion codope tinbase simultaneously Thing, Fe/SnO2Nano composite material and pure phase SnO2The irreversible capacity of gained negative electrode is followed successively by 554mAh/g, 702mAh/ G and 728mAh/g；Due to the successive increase of the specific surface area during doping, this will necessarily cause in SnO2Electrode surface is formed Solid electrolyte film (SEI films) increase, this just preferably explain doping after irreversible capacity increase.
First all discharge curves of three kinds of materials are closely similar.Cathode of lithium battery is in zwitterion codope tin-based oxide Reveal two different discharge platforms, respectively 0.94V and 0.23V；This likely corresponds to SnO2Decomposition and be reduced into Sn and Li2O, and Li-Sn alloying reactions.These processes well and cathode of lithium battery zwitterion codope tin-based oxide CV in reduction peak part 0.90V and 0.21V reduction potentials match.Sn0It is oxidized to Sn2+And higher Sn (SnO)4+, this will Explained from constant-current charge curve and CV curved portions.
As shown in Figure 5：Using the gained cathode of lithium battery zwitterion codope tin-based oxide of embodiment 8 as active material Gained negative electrode shows best cyclical stability.Pure phase SnO2Gained negative electrode capacity drastically declines with the progress of circulation Subtract.Capacity after circulation in 50 weeks decays to 118mAh/g from 1215mAh/g.By contrast, ferro element doping and iron nitrogen are mixed It is miscellaneous to improve SnO2Cyclical stability.Cathode of lithium battery negative electrode obtained by zwitterion codope tin-based oxide provides High first all charge capacities (1167mAh/g), and capacity slowly reduces in preceding cyclic process in 30 weeks.By 50 weeks follow Ring, it is kept approximately constant, and maintains a higher capacity (680mAh/g).
As shown in Figure 6：When electrode material is tested in different current densities from 0.1C to 5C, it can be found that lithium battery The high rate performance of negative pole negative electrode obtained by zwitterion codope tin-based oxide is optimal.Higher current density 0.2C, Under 1C and 5C, cathode of lithium battery negative electrode obtained by zwitterion codope tin-based oxide remains in that higher capacity, point Not Wei 668mAh/g, 615mAh/g and 577mAh/g, this is substantially higher in the theoretical capacity of business Carbon Materials.In different electric currents Under density by 90 weeks circulation and then it is secondary current density is dropped into 0.1C when, cathode of lithium battery zwitterion codope Negative electrode obtained by tin-based oxide can also reach 659mAh/g in the capacity of 100 weeks, close to 96.9% coulombic efficiency.
According to above-mentioned conclusion, we can see that ferro element and nitrogen codope improve SnO2Electrochemistry Can, this may be attributed to diffusion admittance distance, good crystallinity and high conductance that lithium ion is shortened in cyclic process Rate, influenceed by Doped ions.
The foregoing is only a preferred embodiment of the present invention, but protection scope of the present invention be not limited thereto, Any one skilled in the art the invention discloses technical scope in, technique according to the invention scheme and its Inventive concept is subject to equivalent substitution or change, should all be included within the scope of the present invention.

Claims (10)

1. a kind of cathode of lithium battery preparation method of zwitterion codope tin-based oxide, it is characterised in that including as follows Step：
S1, pink salt and molysite are carried out to one step hydro thermal method preparation Fe/SnO2Nano composite material；
S2, by Fe/SnO2Nano composite material be placed in nitrogen atmosphere or ammonia atmosphere sintering obtain cathode of lithium battery negative and positive from Sub- codope tin-based oxide.
2. the preparation method of cathode of lithium battery zwitterion codope tin-based oxide according to claim 1, its feature It is, S1 concrete operations are as follows：Solution A is obtained by pink salt and molysite are soluble in water；By sodium hydroxide it is soluble in water obtain it is molten Liquid B；Solution A is added dropwise in solution B and obtains solution C；Solution C is subjected to hydro-thermal reaction, centrifuged, washing obtains Fe/SnO2Receive Nano composite material.
3. the cathode of lithium battery according to claim 1 or claim 2 preparation method of zwitterion codope tin-based oxide, it is special Sign is, in S1, pink salt is one or more kinds of in butter of tin, stannous chloride, stannous sulfate, sodium stannate, sodium stannite Composition.
4. according to the preparation side of any one of claim 1-3 cathode of lithium battery zwitterion codope tin-based oxides Method, it is characterised in that in S1, molysite is one in frerrous chloride, ferrous sulfate, ferrous nitrate, iron chloride, ferric sulfate, ferric nitrate Kind or two or more compositions.
5. according to the preparation side of any one of claim 2-4 cathode of lithium battery zwitterion codope tin-based oxides Method, it is characterised in that in S1, the mol ratio of tin element, ferro element and sodium hydroxide is 1：60：7.
6. according to the preparation side of any one of claim 1-5 cathode of lithium battery zwitterion codope tin-based oxides Method, it is characterised in that in S1, the temperature of hydro-thermal reaction is 180-200 DEG C, and the time of hydro-thermal reaction is 12-24h.
7. according to the preparation side of any one of claim 2-6 cathode of lithium battery zwitterion codope tin-based oxides Method, it is characterised in that in S1, centrifugal rotational speed 3500-4500r/min.
8. according to the preparation side of any one of claim 1-7 cathode of lithium battery zwitterion codope tin-based oxides Method, it is characterised in that in S2, sintering temperature is 450-550 DEG C, sintering time 8-12h.
9. a kind of cathode of lithium battery zwitterion codope tin-based oxide, it is characterised in that appointed using such as claim 1-8 One cathode of lithium battery is made with the preparation method of zwitterion codope tin-based oxide.
10. cathode of lithium battery zwitterion codope tin-based oxide according to claim 9, it is characterised in that have Hierarchy, its grain diameter are 30-40nm.
CN201710555566.4A 2017-07-10 2017-07-10 Cathode of lithium battery zwitterion codope tin-based oxide and preparation method thereof Pending CN107492652A (en)

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