CN105576223B - A kind of tin oxide base negative electrode material and preparation method thereof with high reversible capacity - Google Patents

A kind of tin oxide base negative electrode material and preparation method thereof with high reversible capacity Download PDF

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CN105576223B
CN105576223B CN201610010298.3A CN201610010298A CN105576223B CN 105576223 B CN105576223 B CN 105576223B CN 201610010298 A CN201610010298 A CN 201610010298A CN 105576223 B CN105576223 B CN 105576223B
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powder
sno
negative electrode
tin oxide
electrode material
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CN105576223A (en
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胡仁宗
欧阳云鹏
朱敏
王辉
鲁忠臣
曾美琴
许辉勇
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South China University of Technology SCUT
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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
    • 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
    • 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
    • H01M4/58—Selection 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
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/626—Metals
    • 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

Abstract

The tin oxide base negative electrode material with high reversible capacity that the invention discloses a kind of, the tin oxide base negative electrode material are a kind of SnO of composite cathode material for lithium ion cell system2- M-C composite powder material, wherein M represents transition metal element, including Mn, Fe, Co, Cu, Ni transition metal, and transition metal M accounts for the 5~30% of mass percentage content；C is graphite carbon material；Carbon material powder C accounts for the 5~50% of mass percentage content, surplus SnO2Powder；The preparation method for the tin oxide base negative electrode material with high reversible capacity that the present invention also provides a kind of.The present invention has the tin oxide base negative electrode material of high reversible capacity, by SnO2Middle addition transition metal M, graphite carbon material C, prepare the good SnO of structural stability2Base composite negative pole material, to obtain longer charge and discharge circulation life；Can also play simultaneously improves SnO2The invertibity of the embedding lithium conversion reaction of cathode improves the embedding lithium of tin oxide base negative electrode material~structural stability of de- lithium process and the electric conductivity of invertibity and electrode material.

Description

A kind of tin oxide base negative electrode material and preparation method thereof with high reversible capacity
Technical field
The invention belongs to technical field of lithium-ion battery, are related to a kind of lithium ion battery material, and in particular to a kind of Lithium ion battery tin oxide (SnO with high reversible capacity2) base composite negative pole material and preparation method thereof.
Background technique
Energy storage of the rapid development of the industries such as novel information mechanics of communication, electric car, smart grid to lithium ion battery More stringent requirements are proposed for capacity, energy density, service life, safety etc..However, receiving existing electrode material specific capacity Low restriction, lithium ion battery is unable to satisfy the application demand in above-mentioned field at present.Therefore, performance of lithium ion battery of new generation Improve the development that will primarily depend upon height ratio capacity electrode material system.Energy based on embedding lithium~de- lithium mechanism lithium ion battery Amount storage depends on Li with release+Insertion and abjection inside positive and negative pole material.Therefore, electrode material Li is improved+It is embedded in and de- Invertibity out is most important to the high-energy density of lithium ion battery and long-life.Especially many height ratio capacity electrode materials Embedding lithium conversion reaction be directed to Li2The generation of O, and how fundamentally to solve Li in material2The Li of O+That deviates from is reversible Property problem, become high-capacity lithium-ion/lithium~air cell and develop one of the crucial science and technology problem faced.
Compared to cathode such as graphite, Sn metals, Sn base oxide has higher lithium storage content, thermal stability and more various The controllable micro-nano structure changed.SnO2Theoretical Mass specific capacity be 1494mAh/g, volume and capacity ratio is more up to 10220mAh/cm3, than Si cathode (9744mAh/cm3) and Li cathode (2277mAh/cm3) will be high.If SnO2Cathode can Practical application will increase substantially the specific capacity and energy density of lithium-ion battery system.Therefore SnO2Base negative electrode material is held It is continuous to become research hotspot.It is different from the embedding lithium reaction mechanism of metal Sn and transition metal oxide, SnO2Embedding lithium pass through two Step reaction is completed: (1) conversion reaction (SnO2+Li+→Sn+Li2O)；(2) alloying reaction (Sn+xLi+←→LixSn).But by In the poorly reversible of conversion reaction, and the volume expansion of alloying reaction is big, so SnO2It is big in the presence of irreversible capacity for the first time, The problems such as stable circulation is poor.
For cyclical stability difference problem, current most effective solution is by the SnO of nanoscale2With various carbon materials It is compound to expect that (graphite, graphene, carbon nanotube/nano fiber, porous/mesoporous carbon etc.) carries out, forms stable micro-nano structure.? This respect, many seminars of especially domestic colleges and universities and research institute have carried out a large amount of work both at home and abroad, are reported at present Some materials system is that have some very excellent cyclical stabilities.It is to be noted that current SnO2Existing for cathode The big problem of irreversible capacity for the first time is still the main reason for hindering Sn base oxide cathode practical application.
From 1997, it was the lithium ion battery (commodity of cathode that Japanese fuji (Fuji) company, which once pushed Sn base oxide, : production and selling STALION).But (graphite cathode is far below since the initial coulomb efficiency of the Sn base oxide cathode is low > 90%, only~63%) and the problem of caused a series of battery performance, production technology and cost etc., so that should The commercial plan of battery proves an abortion.Compared to increasing substantially for cyclical stability, the SnO that is reported up to this point2 The initial coulomb efficiency of negative electrode material is still lower (<~65%), thus is unable to satisfy application request.In addition, be directed to as What improves SnO2The initial coulomb efficiency of cathode and embedding lithium~de- reversible technical research of lithium also seldom have been reported that.Accordingly we To how improving SnO2The initial coulomb efficiency of cathode and embedding lithium~de- lithium invertibity have carried out technical research, according to our early periods Result of study show under electrochemical conditions, SnO2The Li generated after the embedding lithium of cathode2The decomposition of O is not only restricted to its Thermodynamically stable Property.But due to nanometer Sn phase and Li2The mutual insoluble characteristic of O phase, Sn when electrochemistry takes off lithium0/Li2The nano-mixtures such as O needs pass through Sn, O counterdiffusion reaction of two-phase interface can just regenerate SnO2.But the reversible amount for generating SnO2 depends primarily on Sn0/Li2O Interfacial characteristics and nanometer Sn0The scale of phase and its in Li2Degree of scatter in O matrix.Therefore, the recrystallization of nanometer Sn phase and Sn/Li caused by being roughened2O interface reduction is one of the main reason for causing the embedding lithium conversion reaction difference of SnO2 cathode.
The patents such as CN 101800306B and CN103531747B are proposed using carbon coating stannic oxide micro-nano rice flour end system Standby lithium ion battery material, the problems such as having solved volume change of material during embedding lithium, de- lithium.But above-mentioned patent uses Chemical method to be readily incorporated other impurities or element in material, influence the performance of material；Meanwhile carbon coating is used merely Stannic oxide finally can not also solve Li in material2The Li of O+The invertibity problem of abjection.
Summary of the invention
In order to solve SnO2The above problem existing for negative electrode material, the object of the present invention is to provide following material system and systems Preparation Method.
A mesh of the invention is to provide a kind of composite cathode material for lithium ion cell system SnO2~M~C composite granule Material, it is added to the stone of transition metal and C including Mn, Fe, Co, Cu, including Ni in the oxide that Sn base is cathode Black class carbon material, to improve SnO2Embedding lithium~structural stability of de- lithium process and the conduction of invertibity and electrode material Property.
Another object of the present invention is to prepare stable structure by providing an efficient preparation method of relatively economical The good SnO of property2Base composite negative pole material, to obtain long charge and discharge circulation life；It can also be risen realizing object above simultaneously To improvement SnO2The invertibity of the embedding lithium conversion reaction of cathode, improves the effect of its initial coulomb efficiency and reversible capacity.
The technical scheme adopted by the invention is that a kind of tin oxide base negative electrode material with high reversible capacity, the oxygen Change the SnO that tin base cathode material is a kind of composite cathode material for lithium ion cell system2- M-C composite powder material, wherein M generation Table transition metal element, including Mn, Fe, Co, Cu, Ni transition metal, transition metal M account for the 5~30% of mass percentage content； C is graphite carbon material；Carbon material powder C accounts for the 5~50% of mass percentage content, surplus SnO2Powder；
The SnO2Powder is simple substance tin dioxide powder；C is common graphite powder or expanded graphite powder.
Tin oxide base negative electrode material of the present invention with high reversible capacity, it is further characterized in that,
The simple substance stannic oxide purity is 99.9%, and the particle size of simple substance tin dioxide powder is 1~2 micron；
The granular size of the transition metal M is 5~10 microns；
The purity of the common graphite powder or expanded graphite powder is 99.99%；The granular size 1 of the common graphite powder ~2 microns；The granular size of the expanded graphite powder is 0.5~1 micron.
The preparation method for the tin oxide base negative electrode material with high reversible capacity that the present invention also provides a kind of, the preparation side Method sequentially includes the following steps:
Step 1: by the tin dioxide powder, transition metal M, graphite-like carbon materials containing measurement of respective ingredient percent Expect C, the grinding aid that mass percent is mixed-powder 1~7% is added and is stirred mixing；
Step 2: the dusty material being stirred is put into QM3-SP4 planetary ball mill again, abrading-ball in mechanical milling process Quality and mixed-powder material mass ratio be 15:1~50:1；
Step 3: the ball mill revolution of setting ball milling are as follows: 300~500rpm, Ball-milling Time are 10~50 hours；
Step 4: going out tank after the completion of ball milling, the tin oxide base cathode SnO with high reversible capacity can be obtained2- M-C is multiple Close powder body material
The preparation method of tin oxide base negative electrode material of the present invention with high reversible capacity, it is further characterized in that,
The grinding aid that the step 1 is added in mixed-powder material is dehydrated alcohol.
The present invention has the tin oxide base negative electrode material of high reversible capacity, by SnO2Middle addition transition metal M, graphite Class carbon material C, its purpose is to improve SnO2Embedding lithium~de- lithium process structural stability and invertibity and electrode material Electric conductivity.
Compared with prior art, the present invention having the following advantages and beneficial effects:
(1) present invention by carrying out again after first mixing simple substance stannic oxide and transition metal M and graphite-like carbon C raw material The method of ball milling obtains more tiny stannic oxide particle and transition metal M particle, and makes stannic oxide and transition metal M Particles dispersed is uniform, while making stannic oxide and transition metal M particle being more evenly distributed on carbon base body, can more utilize carbon-based The buffering effect and high conductivity of body, can improve cycle performance of battery.
(2) SnO of the present invention in preparation2Grinding aid dehydrated alcohol is added in-M-C composite material, be can be effectively prevented and is received The reuniting effect of meter level stannic oxide particle makes stannic oxide and transition metal M can be good at mixing；And point of even dispersion Cloth brings the relieving effect of carbon base body effectively into play on the matrix of carbon, is provided with and tries hard to keep for good battery performance Barrier.
(3) present invention is in SnO2Transition metal M is added in-M-C composite material, transition metal M mixes with stannic oxide It is even, the electric conductivity for the material that can effectively improve；Meanwhile transition metal M can be with tin dioxide cathode during discharge The nanometer tin of generation forms Sn-M key, so that reunion of nanometer tin during circulating battery is effectively prevented, so that battery has Better cyclical stability.
(4) present invention uses planetary ball mill method, and work efficiency is high, can effectively refine stannic oxide particle.In high-energy ball milling In the process, by the mechanical force generated in mechanical milling process, particle is made to become tiny, to reach nanoscale grade；Nanoscale two Granules of stannic oxide can effectively reduce Volumetric expansion of the electrode in charge and discharge process, be conducive to the stabilization for keeping electrode Property, improve its cycle performance.While so that particle is attenuated small by planetary ball mill method, moreover it is possible to make to generate in the lattice of particle various Defect, dislocation, atom vacancy and distortion of lattice etc., these defects can the great more migration rates of lithium ion.
(5) present invention prepares SnO using planetary ball mill method2- M-C composite material, simple process, high reliablity are easy real Now it is mass produced.
Detailed description of the invention
Fig. 1 is the XRD diagram of SnO2-Mn-Graphite composite material prepared by the embodiment of the present invention 1；
Fig. 2 is specific capacity-voltage performance curve of SnO2-Mn-Graphite composite material prepared by embodiment 1；
Fig. 3 is the cycle performance curve graph of SnO2-Mn-Graphite composite material prepared by embodiment 1；
Fig. 4 is the CV performance chart of SnO2-Mn-Graphite composite material prepared by the embodiment of the present invention 2；
Fig. 5 is the high rate performance curve graph of SnO2-Mn-Graphite composite material prepared by embodiment 2；
Fig. 6 is the XRD diagram of SnO2-Mn-EG composite material prepared by the embodiment of the present invention 3；
Fig. 7 is the backscatter SEM image of SnO2-Mn-EG composite material prepared by embodiment 3；
Fig. 8 is the cycle performance curve graph of SnO2-Mn-EG composite material prepared by the embodiment of the present invention 4；
Fig. 9 is the XRD diagram and Raman figure of SnO2-Fe-Graphite composite material prepared by the embodiment of the present invention 5；
Figure 10 is the backscatter SEM image of SnO2-Fe-Graphite composite material prepared by embodiment 5；
Figure 11 is the cycle performance curve graph of SnO2-Fe-Graphite composite material prepared by embodiment 5；
Figure 12 is the XRD diagram of SnO2-Co-Graphite composite material prepared by the embodiment of the present invention 3；
Figure 13 is the cycle performance curve graph of SnO2-Co-Graphite composite material prepared by the embodiment of the present invention 6；
Figure 14 is the cycle performance curve graph of SnO2-Cu-Graphite composite material prepared by the embodiment of the present invention 7.
Specific embodiment
The following describes the present invention in detail with reference to the accompanying drawings and specific embodiments.
Tin oxide base negative electrode material provided by the invention with high reversible capacity is a kind of lithium ion battery composite cathode The SnO of material system2- M-C composite powder material, wherein M represents transition metal element, including Mn, Fe, Co, Cu, Ni transition gold Belong to, transition metal M accounts for the 5~30% of mass percentage content；C is graphite carbon material；Carbon material powder C accounts for mass percent The 5~50% of content, surplus SnO2Powder.
SnO of the invention2Powder is simple substance tin dioxide powder；C is common graphite powder or expanded graphite powder.
Simple substance stannic oxide purity of the invention is 99.9%, and the particle size of simple substance tin dioxide powder is 1~2 micro- Rice；The granular size of transition metal M is 5~10 microns；The purity of common graphite powder or expanded graphite powder is 99.99%；Commonly 1~2 micron of the granular size of graphite powder；The granular size of expanded graphite powder is 0.5~1 micron.
The preparation method of tin oxide base negative electrode material with high reversible capacity of the invention is, first by simple substance titanium dioxide After tin, transition metal M and the mixing of carbon raw material powder, dehydrated alcohol is added as grinding aid and carries out ball milling, the content of grinding aid is 1%~7% weight percent of mixed-powder, the weight of abrading-ball and the weight ratio of mixed powder are 15:1~50:1, and ball mill turns Number is 300-500rpm, and Ball-milling Time is 10~50 hours.
Embodiment
Embodiment 1
The negative electrode of lithium ion battery SnO of the present embodiment2- Mn-Graphite composite material the preparation method is as follows:
Ball milling: simple substance stannic oxide, manganese powder and common graphite powder are mixed, wherein stannic oxide powder, manganese powder and common The mass ratio of graphite powder is 7:2:1,2% dehydrated alcohol that quality is abrasive material gross mass is added, using planetary ball mill method ball Mill, wherein the mass ratio of stainless steel abrading-ball and mixed powder is 25:1, Ball-milling Time 20h；Obtain negative electrode of lithium ion battery use SnO2- Mn-Graphite composite material, Fig. 1 are the XRD spectrums of the composite material prepared.
Wherein specific step is as follows for planetary ball mill method:
(1) abrading-ball and proportioned starting powder are packed into ball grinder；
(2) ball grinder is vacuumized by vacuum valve, is then charged with argon gas, reach the pressure value in ball grinder 0.12MPa；
(3) planetary ball mill electromechanical source is connected, setting ball milling method is " unidirectional interval operation, timing are shut down " mode, unidirectionally Interval runing time is 30min, timing 30min, and restarting number is 39 times.Ball grinder is set to be fixed on planetary ball mill rack On, carry out planetary type ball-milling.Motor speed 400r/min.
By SnO manufactured in the present embodiment2- Mn-Graphite composite powder, conductive agent super-p and binder CMC press matter Amount is uniformly mixed than 8:1:1 coated on electrode slice is fabricated on copper foil, is dried in vacuo 12h (100 DEG C).In argon atmosphere glove box In, using lithium metal (purity 99.99%) as to electrode, electrolyte is 1mol/L LiPF6Ethylene carbonate (EC)/carbon Dimethyl phthalate (DMC) (volume ratio 1:1) solution, is assembled into button cell and is tested.Test condition are as follows: charging and discharging currents density For 1A/g, charge and discharge are 0.01V~2.4V (vs.Li by voltage+/Li).It tests obtained voltage-capacity curve graph and sees Fig. 2, As shown, reversible capacity is 1122.3mAh/g to composite material manufactured in the present embodiment for the first time, the is recycled to from the 100th time 1000 circulations, there is no any apparent decaying for capacity.
Fig. 3 is circulation-volumetric properties curve of the button cell prepared, as shown, composite wood manufactured in the present embodiment Material shows higher capacity and extremely long cycle life, and capacity is up to 684mAh/g after 1000 circulations.
Embodiment 2
The negative electrode of lithium ion battery SnO of the present embodiment2The preparation method of-Mn-Graphite based composites, in addition to two The mass ratio of stannic oxide powder, manganese powder and common graphite powder be 7:2.5:0.5, Ball-milling Time be 30 hours, remaining with implementation Example 1 is same.
Fig. 4 is the CV performance curve of preceding 5 circulations of the button cell prepared, as shown, in addition to the 1st circulation, 2-5 The CV curve of secondary circulation essentially coincides, and illustrates that the composite material of preparation has good cyclical stability.Fig. 5 is the button electricity prepared The high rate performance curve in pond, as shown in figure 5, having stable specific capacity tribute under the different current density of composite material of preparation It offers, even if reach 2A/g, reversible capacity is still up to 400mAh/g or more.
Embodiment 3
The negative electrode of lithium ion battery SnO of the present embodiment2The preparation method of-Mn-EG based composites, in addition to common stone Ink powder changes into expanded graphite powder (EG), and the mass ratio of stannic oxide powder, manganese powder and expanded graphite powder is 7:2:1, motor Revolution is 500rpm, and Ball-milling Time is 40 hours, and 7% dehydrated alcohol that quality is abrasive material gross mass is added, remaining with reality It is same to apply example 1, Fig. 6 is the XRD spectrum of the composite material prepared.
SnO manufactured in the present embodiment2The backscatter SEM image of-Mn-EG composite powder is shown in Fig. 7, as shown, two after ball milling Tin oxide and manganese metal is evengranular is distributed on carbon base body, there is no agglomerations, this is conducive to give full play to titanium dioxide The high capacity of tin material.
Embodiment 4
The negative electrode of lithium ion battery SnO of the present embodiment2The preparation method of-Mn-EG based composites, in addition to common stone Ink powder changes expanded graphite powder into, and the mass ratio of stannic oxide powder, manganese powder and expanded graphite powder is 7:2.5:0.5, mill ball quality With SnO2The ratio between gross mass of-Mn-C mixed-powder is 50:1, is added outside 1% dehydrated alcohol that quality is abrasive material gross mass, Remaining is same with embodiment 1.
Fig. 8 is circulation-volumetric properties curve of the button cell prepared, as shown, composite wood manufactured in the present embodiment Material shows higher capacity and extremely long cycle life, and reversible capacity is 1353.5mAh/g, capacity after 500 circulations for the first time Up to 562.1mAh/g.
Embodiment 5
The negative electrode of lithium ion battery SnO of the present embodiment2The preparation method of-Fe-Graphite composite material, in addition to manganese Powder changes iron powder into, and the revolution of motor is 300rpm, remaining is same with embodiment 1, Fig. 9 be the composite material prepared XRD spectrum and Raman map.
SnO manufactured in the present embodiment2The backscatter SEM image of-Fe-Graphite composite powder is shown in Figure 10, as shown in Figure 10, Stannic oxide and iron granule are evenly distributed on carbon base body after ball milling, and there is no agglomerations, this is conducive to sufficiently send out Wave the high capacity of tin dioxide material.
Figure 11 is circulation-volumetric properties curve of the button cell prepared, as shown, composite wood manufactured in the present embodiment Material shows higher capacity and extremely long cycle life, and reversible capacity is 1205.8mAh/g, capacity after 600 circulations for the first time Up to 467.5mAh/g.
Embodiment 6
The negative electrode of lithium ion battery SnO of the present embodiment2The preparation method of-Co-Graphite composite material, in addition to manganese Powder changes cobalt powder into, and Ball-milling Time is 10 hours, remaining is same with embodiment 1, and Figure 12 is the XRD spectrum of the composite material prepared.
Figure 13 is circulation-volumetric properties curve of the button cell prepared, as shown, composite wood manufactured in the present embodiment Material shows higher capacity and extremely long cycle life, and reversible capacity is 1016.1mAh/g, capacity after 400 circulations for the first time Up to 1354.6mAh/g.
Embodiment 7
The negative electrode of lithium ion battery SnO of the present embodiment2The preparation method of-Cu-Graphite composite material, in addition to manganese Powder changes copper powder into, and Ball-milling Time is 50 hours, remaining is same with embodiment 1.
Figure 14 is circulation-volumetric properties curve of the button cell prepared, as seen from the figure, composite wood manufactured in the present embodiment Material shows higher capacity and extremely long cycle life, and reversible capacity is 1114.2mAh/g, capacity after 550 circulations for the first time Up to 637.5mAh/g.
Embodiment 8
The negative electrode of lithium ion battery SnO of the present embodiment2The preparation method of-Cu-Graphite composite material, in addition to manganese Powder changes copper powder into, and the mass ratio of stannic oxide powder, copper powder and common graphite powder is 4:4:2, mill ball quality and SnO2-Cu- The ratio between gross mass of Graphite mixed-powder is outside 30:1, remaining is same with embodiment 1.
Composite material manufactured in the present embodiment shows higher capacity and extremely long cycle life, and reversible capacity is for the first time 810mAh/g, 400 times circulation after capacity be up to 536.4mAh/g.
Embodiment 9
The negative electrode of lithium ion battery SnO of the present embodiment2The preparation method of-Cu-Graphite composite material, in addition to manganese Powder is changed to copper powder, and the mass ratio of stannic oxide powder, copper powder and common graphite powder is 4:1:5, mill ball quality and SnO2-Cu- The ratio between gross mass of Graphite mixed-powder is outside 30:1, and Ball-milling Time is 50 hours, remaining is same with embodiment 1.
Composite material manufactured in the present embodiment shows higher capacity and extremely long cycle life, and reversible capacity is for the first time 837.2mAh/g, 350 times circulation after capacity be up to 518.5mAh/g.
Embodiment 10
The negative electrode of lithium ion battery SnO of the present embodiment2The preparation method of-Ni-Graphite composite material, in addition to manganese Powder is changed to nickel powder, and the mass ratio of stannic oxide powder, nickel powder and common graphite powder is 7:0.5:2.5, mill ball quality and SnO2- The ratio between gross mass of Ni-EG mixed-powder is outside 15:1, remaining is same with embodiment 1.
Composite material manufactured in the present embodiment shows higher capacity and extremely long cycle life, and reversible capacity is for the first time 1132.6mAh/g, 400 times circulation after capacity be up to 625.3mAh/g.
Embodiment 11
The negative electrode of lithium ion battery SnO of the present embodiment2The preparation method of-Ni-Graphite composite material, in addition to manganese Powder is changed to nickel powder, and the mass ratio of stannic oxide powder, nickel powder and common graphite powder is 6:3:1, mill ball quality and SnO2-Ni- The ratio between gross mass of Graphite mixed-powder is outside 40:1, remaining is same with embodiment 1.
Composite material manufactured in the present embodiment shows higher capacity and extremely long cycle life, and reversible capacity is for the first time 1088.6mAh/g, 500 times circulation after capacity be up to 524.7mAh/g.
Embodiment 12
The negative electrode of lithium ion battery SnO of the present embodiment2The preparation method of-Ni-EG composite material, in addition to manganese powder is changed to Nickel powder, common graphite change expanded graphite into, and the mass ratio of stannic oxide powder, nickel powder and expanded graphite powder is 6:2:2, abrading-ball matter Amount and SnO2The ratio between gross mass of-Ni-EG mixed-powder is outside 45:1, remaining is same with embodiment 1.
Composite material manufactured in the present embodiment shows higher capacity and extremely long cycle life, and reversible capacity is for the first time 1125.2mAh/g, 300 times circulation after capacity be up to 736.6mAh/g.
Above embodiment is some preferable embodiments of the invention, but embodiments of the present invention are not intended to The implementation and interest field of invention are limited, what content described in all ranges of patent protection according to the present invention and principle were made etc. Effect variation and modification, substitution, combination, simplify, should be equivalent substitute mode, be included in protection scope of the present invention it It is interior.

Claims (3)

1. a kind of tin oxide base negative electrode material with high reversible capacity, which is characterized in that the tin oxide base negative electrode material is A kind of SnO of composite cathode material for lithium ion cell system2- M-C composite powder material, wherein M represents transition metal element, packet Mn, Fe, Co, Ni transition metal are included, transition metal M accounts for the 5~30% of mass percentage content；C is graphite carbon material, carbon materials Feed powder end C accounts for the 5~50% of mass percentage content, surplus SnO2Powder；
The SnO2Powder is simple substance tin dioxide powder；C is common graphite powder or expanded graphite powder；
A kind of preparation method of tin oxide base negative electrode material with high reversible capacity sequentially includes the following steps:
Step 1: by the tin dioxide powder, transition metal M, graphite carbon material C containing measurement of respective ingredient percent, The grinding aid that mass percent is mixed-powder 1~7% is added and is stirred mixing；
Step 2: the dusty material being stirred is put into planetary ball mill again, the quality of abrading-ball and mixed in mechanical milling process The mass ratio for closing dusty material is 15:1~50:1；
Step 3: the ball mill revolution of setting ball milling are as follows: 300~500rpm, Ball-milling Time are 10~50 hours；
Step 4: going out tank after the completion of ball milling, the tin oxide base cathode SnO with high reversible capacity can be obtained2- M-C composite granule Material.
2. the tin oxide base negative electrode material according to claim 1 with high reversible capacity, which is characterized in that the simple substance Stannic oxide purity is 99.9%, and the particle size of simple substance tin dioxide powder is 1~2 micron；
The granular size of the transition metal M is 5~10 microns；
The purity of the common graphite powder or expanded graphite powder is 99.99%；The granular size 1~2 of the common graphite powder Micron；The granular size of the expanded graphite powder is 0.5~1 micron.
3. a kind of preparation method of the tin oxide base negative electrode material with high reversible capacity according to claim 1, feature It is, the grinding aid that the step 1 is added in mixed-powder material is dehydrated alcohol.
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CN106654181A (en) * 2017-03-01 2017-05-10 欣旺达电子股份有限公司 Tin oxide-based negative electrode material and preparation method therefor
CN107331854B (en) * 2017-08-23 2020-02-11 吉林大学 Composite electrode material with multi-stage nanostructure and prepared by coating carbon fiber loaded with metal nanoparticles with transition metal oxide
CN109411717A (en) * 2018-09-28 2019-03-01 华南理工大学 A kind of negative electrode material and preparation method thereof through prelithiation with high reversible capacity
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