CN105118966B - A kind of high nitrogen-containing tin carbon composite for cathode of lithium battery and preparation method - Google Patents

A kind of high nitrogen-containing tin carbon composite for cathode of lithium battery and preparation method Download PDF

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CN105118966B
CN105118966B CN201510600582.1A CN201510600582A CN105118966B CN 105118966 B CN105118966 B CN 105118966B CN 201510600582 A CN201510600582 A CN 201510600582A CN 105118966 B CN105118966 B CN 105118966B
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composite
solution
diaminomaleonitrile
cathode
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CN105118966A (en
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李忠涛
邓深圳
王书敬
王元坤
吴明铂
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China University of Petroleum UPC East China
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    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of or comprising active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/362Composites
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of or comprising active material
    • H01M4/13Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139Processes of manufacture
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of or comprising active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/48Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of or comprising active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/58Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/5835Comprising fluorine or fluoride salts
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries

Abstract

The present invention relates to a kind of composite for cathode of lithium battery, use the method as dressing agent, graphite oxide being carried out N doping by diaminomaleonitrile (DAMN) to be prepared from.SnCl is added during N doping4·5H2O, forms the composite construction of carbonitride and tin oxide by high temperature cabonization.The present invention uses the controlled SnO preparing high nitrogen content of one step hydro thermal method2/CxNy/ GN composite, shows good chemical property when this composite is used for lithium ion battery negative.SnO2The nanoscale dispersion of particle and the cross-linked polymeric of surface and nitrogen-doped graphene thereof.The introducing of diaminomaleonitrile not only increases the electric conductivity of graphite oxide, provides more reaction active site and SnO simultaneously2Nanocrystalline reaction, makes SnO2Being dispersed in carbonitride and graphene sheet layer of nanoparticles stable.

Description

A kind of high nitrogen-containing tin carbon composite for cathode of lithium battery and preparation method
Technical field
The present invention relates to the preparation of composite, particularly to a kind of answering for cathode of lithium battery Condensation material.
Background technology
Lithium ion battery is owing to having that monomer voltage is high, energy density big, have extended cycle life, pacifying The advantages such as loopful guarantor, and be widely used in various electronic product.The performance of lithium ion battery Depend primarily on the performance of positive and negative electrode material.Therefore, the raising of performance of lithium ion battery is main Depend on the raising of positive and negative electrode material property.
The negative material of current business-like lithium ion battery is graphite-based negative material.But graphite Base negative material capacity is low, voltage delay, can not meet the demand of people.And transition metal Oxide has higher theoretical specific capacity, but it is susceptible to swollen at charge and discharge process volume Swollen, cause cyclical stability poor.In order to overcome these shortcomings, people concentrate on to study to be had simultaneously There is the lithium ion battery negative material of high specific capacity and cyclical stability.In these are studied, SnO2High theoretical capacity (782mAh g in cyclic process-1), attract a lot Pay close attention to.Carbon cladding tin oxide negative material can show in combination with carbon and the respective advantage of tin Excellent performance.But, current carbon encapsulated material, due to the nanoparticle that it is the most uneven Low electric conductivity with carbon coated so that it is capacity holding capacity is the most limited.And before some The method preparing carbon encapsulated material is relative complex.Therefore find a kind of simple and can ensure simultaneously SnO2The method of the structure of the carbon base body of the dispersed and conduction of nanoparticle, has important Meaning.
Find there is hetero atom (such as boron, nitrogen, sulphur, phosphorus etc.) and adulterate according to research before Material with carbon element has higher specific capacity and more preferable cyclical stability than unadulterated material with carbon element.And In these hetero atoms, owing to the electronegativity of nitrogen is bigger than carbon, atomic radius is less than carbon, and adulterate nitrogen Atom will fill up the defective bit in graphite oxide conjugated system, simultaneously by graphene sheet layer Oxygen-containing functional group is converted to be conjugated regularity higher C=N key.Some amino-compounds contain The higher group of activity, while improving graphite oxide electric conductivity, also be graphene oxide and The more reaction active site of compound offer of inorganic material.Therefore, nitrogen-doped carbon material is to have very much The lithium ion battery electrode material of application prospect.
Summary of the invention
For defect present in prior art, it is an object of the invention to provide a kind of for lithium electricity Composite of pond negative pole and preparation method thereof.
The present invention is achieved through the following technical solutions:
A kind of composite for cathode of lithium battery, use by cyano-containing and amino is organic Thing, pink salt and three kinds of raw materials of graphite oxide are prepared from.
On the basis of such scheme, the organic matter of described cyano-containing and amino is diaminourea Malaysia Nitrile.
On the basis of such scheme, described pink salt is SnCl4 5H2O.
On the basis of such scheme, graphite oxide is ultrasonic disperse in distilled water, is aoxidized Graphene solution.
On the basis of such scheme, the concentration of described graphite oxide solution alkene is 0.3-3.0 mg·mL-1
On the basis of such scheme, under conditions of graphene oxide solution is heated to 30-60 DEG C Add diaminomaleonitrile.
On the basis of such scheme, diaminomaleonitrile adds after being completely dissolved SnCl4·5H2O。
On the basis of such scheme, SnCl4·5H2O is completely dissolved rear mixed liquor and exists 8-20h is reacted under the conditions of 120-180 DEG C.
On the basis of such scheme, described reaction is carried out in water heating kettle.
On the basis of such scheme, product is washed dried at 400-600 DEG C by centrifugation Calcining more than 2h.
On the basis of such scheme, calcining is to carry out under atmosphere of inert gases.
The invention has the beneficial effects as follows:
The present invention uses the controlled SnO preparing high nitrogen content of one step hydro thermal method2/CxNy/ GN is combined Material, shows good electrochemistry when this composite is used for lithium ion battery negative Energy.SnO2The nanoscale dispersion of particle and the cross-linked polymeric of surface and nitrogen-doped graphene thereof. The introducing of diaminomaleonitrile not only increases the electric conductivity of graphite oxide, provides more simultaneously Reaction active site and SnO2Nanocrystalline reaction, makes SnO2Nanoparticles stable dispersed In carbonitride with graphene sheet layer.
Accompanying drawing explanation
The present invention has a drawings described below:
Fig. 1 is SnO2/CxNy、SnO2/ DAMN/GO and SnO2/CxNyThe XRD of/GN Collection of illustrative plates, wherein (a) SnO2/CxNyXRD (b) SnO2The XRD of/DAMN/GO Figure (c) SnO2/CxNyThe XRD of/GN;
Fig. 2 is SnO2/CxNy、SnO2/ DAMN/GO and SnO2/CxNyThe TEM of/GN Figure and SnO2/CxNyThe HR-TEM figure of/GN, wherein (a) SnO2/CxNyTEM Figure (b) SnO2The TEM of/DAMN/GO schemes (c) SnO2/CxNyTEM figure (d) of/GN SnO2/CxNyThe HR-TEM figure of/GN;
Fig. 3 is SnO2/CxNy、SnO2/ DAMN/GO and SnO2/CxNyThe FT-IR of/GN Collection of illustrative plates, wherein (a) SnO2/CxNyFTIR scheme (b) SnO2The FTIR of/DAMN/GO Figure (c) SnO2/CxNyThe FTIR figure of/GN;
Fig. 4 is SnO2/CxNyThe aerial TGA of/GN schemes;
Fig. 5 is SnO2/CxNy、SnO2/ DAMN/GO and SnO2/CxNy/ GN is at 100mA g-1Current density under stable circulation performance and SnO2/CxNyThe coulombic efficiency figure of/GN;
Fig. 6 is SnO2/CxNy、SnO2/ DAMN/GO and SnO2/CxNyThe exchange resistance of/GN Anti-figure;
Fig. 7 is SnO2/CxNyThe high rate performance figure of/GN material;
Fig. 8 is SnO2/CxNyThe cyclic voltammetric of/GN and capacity voltage pattern;
Detailed description of the invention
Below in conjunction with accompanying drawing, the present invention is described in further detail.
Embodiment 1
First with graphite powder by the Hummers method synthesis graphite oxide optimized.By 200mg Graphite oxide is ultrasonic disperse 2 hours in 200ml distilled water, form graphene oxide solution, The solution liquid obtained is labeled as solution A.Solution A is heated to 45 DEG C, and stirring is lower slowly Add 0.80g diaminomaleonitrile so that it is fully dissolving, the solution obtained is designated as solution B. Under stirring, by 1.20g SnCl4·5H2O is dissolved in above-mentioned solution B.Then, mixed liquor is shifted To water heating kettle, hydro-thermal 12 hours at 150 DEG C.After reaction, naturally it is down to room temperature.By institute Obtaining product centrifuge washing for several times, product is dried at 70 DEG C.Finally, at high purity N2Atmosphere Under tube furnace in 500 DEG C calcine 2 hours, i.e. can get SnO2/CxNy/ GN composite. By above-mentioned identical method, prepare the composite wood being not added with graphite oxide and non-carbonization treatment respectively Material, is respectively labeled as SnO2/CxNyAnd SnO2/DAMN/GO。
Analysis and characterization
Employing Holland X ' Pert PRO MPD type X-ray diffractometer (XRD, CuK α, λ=0.15406nm) sample is carried out structure, material phase analysis.Use Germany STA 409PC The tin ash content of Luxx thermogravimetric analyzer (TGA) test sample in air atmosphere.Pass through Saturating with JEM-2100UHR type with Japan Hitachi S-4800 type SEM (SEM) Penetrate electron microscope (TEM) and observe pattern and the structure of sample.Contained element and sense in sample Group is by U.S. Thermo Nicolet NEXUS 670 type examination of infrared spectrum instrument (FT-IR) point Analysis.
Result and analysis:
Fig. 1 (a), (b), (c) have five wider diffraction maximums, is respectively belonging to SnO2 (110), (101), (200), (211) and (301) crystal face diffraction (JCPDS No.41-1445). Wide in range diffraction maximum shows SnO in prepared composite2It is held at less size.From It is also found that (c) is compared with (a) in figure, after adding Graphene, the peak width of diffraction maximum becomes Greatly, illustrate that the addition of Graphene promotes the dispersion of granules of stannic oxide.(c) compared with (b), After high-temperature heat treatment, the peak width of diffraction maximum diminishes, and illustrates that high-temperature heat treatment makes granules of stannic oxide Reunite.
For verifying the microstructure of composite further, three kinds of composites are done transmission electricity Mirror test (shown in Fig. 2).In Fig. 2, (c) compares with (b) figure, and tin oxide particle diameter becomes big, Illustrating after high temperature cabonization, there is slight reunion in tin oxide grain.(c) and (a) figure Comparing, the dispersiveness adding Graphene rear oxidation tin particles has obtained obvious improvement, and stone is described The addition of ink alkene can promote the dispersion of tin oxide.This is phase one with the characterization result of XRD spectrum (as shown in Figure 1) caused.SnO2/CxNyThe nanostructured of/GN is further characterized by height Resolution transmission electron microscope (HR-TEM), as shown in Fig. 2 (c), SnO2Nanometer Grain is evenly dispersed on the surface of carbonitride.The illustration of Fig. 2 (d) can clearly be sent out Existing SnO2Lattice fringe.Spacing of lattice is that the lattice fringe of 0.323nm and 0.230nm divides Not correspond to SnO2(110) and (200) crystal face.
The structure change of reducing degree and carbon nitride material in order to characterize graphene oxide, will Sample has carried out Fourier transform infrared spectroscopy test (such as Fig. 3).It is known that oxidation stone Ink alkene is at following infrared absorption peak: 1740cm-1Place correspond to-COOH, at 1401cm-1Right Answer O-H, at 1220cm-1Correspond to C-OH, 827 and 1052cm-1Correspondence respectively O-C=O and C-O, it addition, at 1620cm-1There is a SP at place2The characteristic feature of C=C Peak.In Fig. 3, at 617cm in the infrared spectrogram of three samples-1Have one obvious red Outer absworption peak, this is owing to the stretching vibration of Sn-O.Sample in (b) figure SnO2/ DAMN/GO contains the infrared absorption peak of-COOH ,-CHO and O-H, and (c) Figure sample SnO2/CxNyBeing not detected by in/GN, this is owing to the graphene oxide in sample exists Reduced after high-temperature process.Furthermore, it is possible to find sample SnO2/DAMN/GO At 2270cm-1There is the strongest-C ≡ N peak, and at sample SnO2/CxNy/ GN and SnO2/CxNy In become the most weak, and at 1300cm-1Place creates C-N peak, at 1630cm-1Place Create C=N peak, the formation having carbonitride after high temperature cabonization is described.Sample SnO2/CxNy/ GN and SnO2/CxNyCurve in 900cm-1~600cm-1Absworption peak becomes Ratio sample SnO2/ DAMN/GO becomes apparent from, and this is owing to aromatic compound increases caused. Therefore, sample can form carbonitride conjugated conductive network through higher heat treatment temperature, and And at high temperature graphite oxide can more thoroughly be reduced to Graphene.This ties with AC impedance spectrogram Fruit is consistent (as shown in Figure 6).
In order to obtain SnO2/CxNyThe content of tin oxide in/GN composite, enters this sample Go thermal weight loss test (such as Fig. 4).Understanding according to Fig. 4, before 300 DEG C, composite is only Slight mass loss, illustrates that the carbon in composite and tin oxide are in atmosphere to 300 DEG C of temperature Degree still remains chemical stability.300-550 DEG C of mass loss is obvious, and this is owing to nitridation Carbon and the reaction of Graphene aerial vigorous combustion.Finally, only SnO2Particle can be by Retain.According to SnO2/CxNyThe TGA curve of/GN, the tin oxide content in derived sample It is about 38%.
Comprehensive above analysis is it is inferred that the present invention the most successfully prepares SnO2/CxNy/GN Composite.
Electrochemical property test
Weighed above-mentioned composite sample (active material), acetylene black by the mass ratio of 8: 1: 1, gathered Vinylidene (PVDF) (PVDF is dissolved in 1-METHYLPYRROLIDONE in advance), three is uniform It is mixed to form slurry;By slurry even application on Copper Foil.Pole piece is put in vacuum drying chamber After 100 DEG C of dry 10h, the thin slice being cut into a diameter of 16mm makes pole piece.With lithium metal it is To electrode, making CR2032 type button cell in the glove box of full argon gas, barrier film uses U.S. State Celgard2400, electrolyte uses LiPF6/ EC: DEC (1:1 volume ratio).Use The charge-discharge performance of LandCT2001A battery test system test sample, discharge and recharge final voltage For 0.005-2.5V.Cyclic voltammetry uses Ametek PARSTAT4000 electrochemistry work Making station test, sweep speed is 0.2mV s-1, voltage range 0.01-2.5V.
Fig. 5 is SnO2/CxNy、SnO2/ DAMN/GO and SnO2/CxNy/ GN is at 100mA g-1Current density under stable circulation performance and SnO2/CxNyThe coulombic efficiency figure of/GN.By Fig. 5 understands, SnO2/CxNy、SnO2/DAMN/GO、SnO2/CxNyTri-samples of/GN First charge-discharge specific capacity is respectively 850.6/1811.3mAh g-1、985.8/2338.8 mAh·g-1、1164.1/2556.6mAh·g-1.Three samples have one in discharge process first Individual bigger irreversible capacity loss, respectively 53.0%, 57.8% and 54.4%, this returns Because of in the formation of solid electrolyte film (SEI film) and SnO2Decomposition.SnO2/CxNy、 SnO2/DAMN/GN、SnO2/CxNy/ GN through 50 times circulation after capacity retention rate (with Second time is compared) it is respectively 16.5%, 54.1% and 69.4%.It should be noted that SnO2/CxNy/ GN sample special capacity fade after 100 circulations is little, remains in that At 730mAh g-1Left and right.
As shown in Figure 5, SnO2/CxNyThe coulombic efficiency of/GN sample is all protected in addition to first twice Hold about 100%, it is shown that the electrochemical reversibility that this material is good.SnO2/CxNy/GN Good chemical property is owing to SnO2Nano particle being uniformly distributed in carbonitride (XRD and TEM is proved).It addition, not only help conductive network by heat treatment Building, and graphene oxide can be made more thoroughly to reduce, both of which can dramatically increase The electric conductivity of composite.On the contrary, SnO2/CxNyThe capacity attenuation of sample is very fast, and this can Can be due to granules of stannic oxide poor dispersion in carbonitride and material electric conductivity Poor.
For proving the electric conductivity of three kinds of composites further, they are carried out AC impedance survey Examination (such as Fig. 6).Fig. 6 is the AC impedance figure of sample obtained by three different materials, exchange Impedance curve is the semicircle by high frequency region and the rectilinear(-al) of low frequency range.Half circular diameter of high frequency region The least, the resistance of sample is the least.It can be seen that SnO2/CxNy/ GN has minimum Resistance.The formation that this explanation high temperature cabonization contributes to carbonitride conjugate network is (red with Fourier Outer test result is consistent, as shown in Figure 3), improves the electric conductivity of material.It addition, graphite The addition of alkene also substantially increases the electric conductivity of material.
Fig. 7 is SnO2/CxNyThe rate charge-discharge cycle performance figure of/GN composite.By scheming Understand, again return to 100mA g through different current density discharge and recharges-1Current density, its Remain to return to 750mA g than taking in-1Left and right.Material after high current charge-discharge is described Structure is also not corrupted, and the stability of material is fine.
SnO in sum2Why-S/N-GNs composite presents the most excellent electrification Learning performance, return its reason mainly to have following three points: first, N doped graphene is coated on SnO2 Nanoparticle size is peripheral, effectively inhibits SnO in cyclic process2Volumetric expansion problem; Secondly, introducing the diaminomaleonitrile containing greater activity group, after high temperature cabonization, crosslinking is poly- The cancellated carbonitride of synthesis of conjugate, while improving graphite oxide electric conductivity, is also oxygen Functionalized graphene and the more reaction active site of compound offer of inorganic material, increase composite Chemical property;It addition, Graphene there was added beneficially SnO in course of reaction2Nano particle Dispersion, it is possible to obtain the nano particle that particle size is less, embedding lithium/de-lithium process can be slowed down In Volumetric expansion, promote ion transportation.
In order to study the energy storage mechnism of this composite further, this composite is assembled into electricity Pond has carried out cyclic voltammetry (as shown in Figure 8).It is observed that from Fig. 8 (a) Once circulation there are a weak irreversible reduction peak, this peak following below near 0.6V Not occurring in ring, this divides owing to formation and the tin oxide of solid electrolyte film (SEI film) Solve the process for metallic tin.Putting near 0.6V on discharge curve first in this peak and Fig. 8 (b) Level platform is corresponding.As shown in formula (1):
SnO2+4Li++4e-→2Li2O+Sn (1)
Reduction peak clearly near 0.22V and the oxidation peak near 0.54V respectively with tin, The alloy reaction of lithium and Sn are from LixSn alloy is removed relevant.As shown in formula (2):
Sn+xLi++xe-←→LixSn(0≤x≤4.4) (2)
This paper is with SnCl4·5H2O, diaminomaleonitrile and graphite oxide are that raw material is through hydro-thermal The carbonitride combined oxidation tin material having three's advantage concurrently has been prepared with high-temperature process.Experiment number According to showing, this material list reveals the chemical property of excellence: at 100mA g-1Current density Under, 100 specific capacities of constant current charge-discharge circulation remain to maintain 730mAh g-1Left and right.This reality Proved recipe method is simple, gentle, economic and environment-friendly, opens up for exploitation large-capacity and high-performance lithium ion battery One new path.

Claims (5)

1. the composite for cathode of lithium battery, it is characterised in that: use and be prepared from by the ratio of cyano-containing and the organic matter of amino, pink salt and three kinds of raw material 4:6:1 in mass ratio of graphite oxide;The organic matter of described cyano-containing and amino is diaminomaleonitrile, and described pink salt is SnCl4·5H2O。
The preparation method of a kind of composite for cathode of lithium battery the most according to claim 1, it is characterised in that comprise the steps:
(1) by graphite oxide ultrasonic disperse in distilled water, obtain graphene oxide solution, the solution obtained is labeled as solution A;
(2) solution A being heated to 30-60 DEG C, be slowly added to diaminomaleonitrile so that it is fully dissolve under stirring, the solution obtained is designated as solution B;
(3) stirring under, diaminomaleonitrile be completely dissolved after by SnCl4·5H2O is dissolved in above-mentioned solution B;
(4) SnCl4·5H2After O is completely dissolved, mixed liquor is made to react 8-20 h under the conditions of 120-180 DEG C;
(5), after reaction, room temperature naturally it is down to;Product is washed by centrifugation and is calcined more than 2 hours at 400-600 DEG C after drying;I.e. can get SnO2/CxNy/ GN composite.
Method the most according to claim 2, it is characterised in that: graphene oxide solution concentration described in step (1) is 0.3-3.0 mg mL-1
Method the most according to claim 3, it is characterised in that: react described in step (4) and carry out in water heating kettle.
Method the most according to claim 2, it is characterised in that: described in step (5), calcining is to carry out under atmosphere of inert gases.
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CN108123126A (en) * 2017-12-20 2018-06-05 厦门紫阳科技产业发展有限公司 A kind of preparation method of high-capacity lithium ion cell stannic oxide/nitrogen-doped graphene composite negative pole material
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