CN106946285B - A kind of lithium battery fibrous porous oxidation tin negative pole material and preparation method - Google Patents

A kind of lithium battery fibrous porous oxidation tin negative pole material and preparation method Download PDF

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CN106946285B
CN106946285B CN201710164813.8A CN201710164813A CN106946285B CN 106946285 B CN106946285 B CN 106946285B CN 201710164813 A CN201710164813 A CN 201710164813A CN 106946285 B CN106946285 B CN 106946285B
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陈庆
曾军堂
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Weihai Nanhai new energy materials Co., Ltd.
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    • H01M10/0525Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • H01M4/485Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
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Abstract

The present invention relates to lithium battery material fields, and in particular to a kind of fibrous porous oxidation tin negative pole material and preparation method for lithium battery.By disperseing sodium chloride crystal grain in advance in tin, sodium chloride is distributed with grain form in the nano wire formed after spinning, further aoxidized by second order, stannum nanowire is set to be converted into tin oxide nano-wire, the sodium chloride crystal grain for being doped in tin simultaneously melts to form crystal grain defective hole, hole defect is aoxidized, so that tin oxide nano-wire is covered with uniform through hole.This fibrous tin oxide with through hole can be embedded in more lithium ion, improve the energy density of battery.And solve tin oxide volume expansion during charge and discharge cycles and shrink caused dusting, so that the loss of capacitance of tin oxide is substantially lowered.

Description

A kind of lithium battery fibrous porous oxidation tin negative pole material and preparation method
Technical field
The present invention relates to lithium battery material fields, and in particular to a kind of fibrous porous oxidation tin negative pole material of lithium battery And preparation method.
Background technology
With rapid development of economy, facing mankind energy crisis and the severe challenge of environmental pollution, and countries in the world are all Constantly seek the green energy resource of more clean environment firendly.Wherein, lithium battery is since it is high with energy density, voltage is high, the cycle longevity The advantages that life is long, self-discharge rate is low, memory-less effect, discharge voltage are stable, charge and discharge are quick and environmentally friendly, is widely used in moving Power battery.The positive electrode research of lithium battery is relatively more, no matter from the selection of material category or is modified, has all reached higher Level.With the development of positive electrode, the application especially in power battery, the existing negative material based on carbon is more next The needs of more inadaptable development.Main body of the negative material as storage lithium, capacity and stability are the key that influence performance.
Currently, the lithium ion battery of commercialization mainly uses graphite or modified graphite as negative material.However, graphite Theoretical embedding lithium maximum capacity is only 372mAh/g, and irreversible loss is big for the first time, multiplying power discharging property is poor, in addition, in lithium ion When embedded, the partial solvent of electrolyte can also follow insertion, be easy to happen the variation of structure.Obviously it cannot meet automobile-used lithium ion Battery is high-power, high power capacity requirement.Therefore, in field of lithium, it is badly in need of the update of negative material at present.
Have studies have shown that the oxidation of nanometer transition metal has higher theoretical specific capacity, and capacity retention ratio is high, such as The oxide of silicon, titanium, tin etc. becomes the hot spot of research.But this kind of transition metal oxide material is lithium ion is embedded and abjection Larger volume expansion and contraction change are had in the process, so as to cause the dusting of electrode material, and then lose electricity with collector Contact, the cycle performance of the such material of strong influence and application.
Tin oxide is because with height ratio capacity (theoretical charge/discharge capacity is 790mAh/g), low embedding lithium potential, security performance The advantages that good and receive much attention, and tin oxide is resourceful, and cheap, environmental pollution is small, be expected to substitute carbon material at For novel lithium battery cathode material.But tin oxide equally exists serious bulk effect during embedding de- lithium, charge and discharge for the first time Electric expansion shrinking percentage is up to 50% or more, and dusting easily occurs during the repeatedly embedded and abjection of lithium ion during cycle and show As so as to cause tin oxide, irreversible capacity is larger for the first time, and chemical property declines rapidly, and cyclical stability is poor, limits Its extensive use in lithium ion battery.
Technical staff attempts to improve its performance by the granular size and pattern of change tin oxide, such as nanobelt, nanometer Line, nano-particle, hollow ball etc..Shorten the transmission range of electronics, ion by nanosizing, increases electrode/electrolyte interface Area, especially can buffer volumes variation caused by stress, and then improve electrode material cyclical stability.Such as Chinese invention Patent CN 103708535B disclose a kind of carbon doped stannic oxide nanometer line lithium cell cathode material, by making tin oxide nano Line can improve storage lithium ability and lithium ion diffusion rate, alleviate the influence of volume change.But fail fundamentally to solve Powder phenomenon-tion caused by volume expansion and contraction change.
Invention content
For tin oxide for cathode of lithium battery there are volume expanding powder, loss of capacitance is big, defect of short life, this Invention proposes a kind of fibrous porous oxidation tin negative pole material for lithium battery, it is characterized in that tin oxide is nano-scale fiber Shape is covered with uniform through hole on single fiber, which generated by crystal grain defect, on the one hand has tin oxide excellent Different electronics conduction function, the embedding lithium of another aspect are happened at through hole, and the volume expansion for effectively inhibiting tin oxide is shunk, same Deng under the conditions of, it can be embedded in more lithium ion, improve the energy density of battery.Efficiently solve common nano wire tin oxide capacitance Amount loses big, short life defect.Another object of the present invention is to provide a kind of fibrous porous oxidations for lithium battery The preparation method of tin negative pole material.
To solve the above problems, the present invention uses following technical scheme:
A kind of fibrous porous oxidation tin negative pole material for lithium battery, it is characterized in that tin oxide is nano-scale fiber Shape is covered with uniform through hole on single fiber, and the through hole is for crystal grain defective hole.
A kind of preparation method of fibrous porous oxidation tin negative pole material for lithium battery, specific preparation process is such as Under:
(1)By powdered sodium chloride and glass putty with mass ratio 10:100-300 is uniformly mixed, and is then fed into screw extruding The temperature of machine, setting Screw Extrusion press is 220-230 DEG C, makes sodium chloride grind to be formed by the rotational shear of screw rod, dispersion Crystal grain is simultaneously dispersed in the tin of semi-molten state and forms doped tin;
(2)By step(1)Obtained doped tin is sent into high temperature and pressure homogenizer while hot, and setting temperature is 300-350 DEG C, high Body of calming the anger is nitrogen, by homogenizer high temperature and pressure, so that doped tin is formed injection stream and enters high voltage electrostatic spinning, obtain radial direction For the nano wire of Nano grade;
(3)By step(2)Obtained nano wire is sent into two stepwise fluid beds, and the first rank fluidized-bed temperature of setting is in 150- Between 200 DEG C, so that nano wire is quickly aoxidized in complete suspended state lower surface by sufficient air, react 10-30s, formed The nano wire of surface oxidation;Subsequently into second-order fluid bed, setting second-order fluidized-bed temperature leads between 800-810 DEG C Crossing sufficient air makes nano wire quickly be aoxidized under complete suspended state, and the sodium chloride crystal grain for being doped in tin with this condition is molten Melt to form crystal grain defective hole, while tin is aoxidized, so that tin oxide nano-wire is covered with uniform through hole;
(4)By step(3)Obtained material is cleaned with deionized water, removes remaining sodium chloride, and drying, refinement obtain Fibrous porous oxidation tin negative pole material for lithium battery.
Preferably, step(1)The screw extruder is twin (double) screw extruder.
It is further preferred that step(1)The screw extruder is parallel dual-screw extruder, and significant advantage is It is preferably ground to micromeritics with strong shear divergent function, by sodium chloride and is dispersed in semi-vitreous tin.
Preferably, step(2)The pressure of the high temperature and pressure homogenizer is set as 3-5MPa, to form powerful injection Stream makes spinning reach nanoscale.
Preferably, step(3)It is 15s in the reaction time of the first rank, which preferably ensures that tin surfaces are quick It forms relatively thin stannic oxide layer and is unlikely to nano wire deformation.
A kind of fibrous porous oxidation tin negative pole material for lithium battery of the invention, by disperseing chlorination in advance in tin Sodium crystal grain, sodium chloride is distributed with grain form in the nano wire formed after spinning, is further aoxidized by second order, is made stannum nanowire The sodium chloride crystal grain for being converted into tin oxide nano-wire, while being doped in tin melts to form crystal grain defective hole, and hole defect is aoxidized, from And tin oxide nano-wire is made to be covered with uniform through hole.This fibrous tin oxide with through hole can be embedded in more lithium Ion improves the energy density of battery.And it solves tin oxide volume expansion during charge and discharge cycles and shrinks caused powder Change, the loss of capacitance of tin oxide is made substantially to lower.
One typical application is the fibrous porous oxidation tin negative pole material for obtaining the present invention and lithium manganate cathode material Material composition battery testing group, battery performance test the results show that prepare electrode material for the first time discharge capacity be 725 mAh/g, Capacity is 690mAh/g after recycling 300 times, and capacity retention ratio is more than 90%.Therefore, micro- by forming perforation in tin oxide fibre Hole fundamentally solves defect of the tin oxide as cathode of lithium battery capacity attenuation.
A kind of fibrous porous oxidation tin negative pole material and preparation method for lithium battery of the invention, with prior art phase Than the feature and excellent effect protruded is:
1, the fibrous porous oxidation tin negative pole material of the present invention has been covered with uniformly by through hole, no on each single fiber But it can be embedded in more lithium ion, and volume change during charge and discharge cycles is obviously inhibited, effectively solved Common nano wire tin oxide loss of capacitance of having determined is big, short life defect.
2, the present invention passes through pre-doping sodium chloride crystal grain so that the other defect of die level is formd on tin oxide nano-wire Hole, method is simple and practicable, and defective hole is uniformly stablized, and industrialized production is suitable for.
Description of the drawings
Fig. 1 is the scanning electron microscope (SEM) photograph of the fibrous porous tin oxide of the present invention.
Specific embodiment:
Detailed description below is described in further detail the above of the present invention again.But this should not be managed Solution is only limitted to example below for the range of the above-mentioned theme of the present invention.Without departing from the idea case in the present invention described above, root The various replacements or change made according to ordinary skill knowledge and customary means, should all be included within the scope of the invention.
Embodiment 1
(1)By powdered sodium chloride and glass putty with mass ratio 10:100 are uniformly dispersed in high speed dispersor, then send Enter 38 type parallel dual-screw extruding machines, the temperature of setting Screw Extrusion press is 220-230 DEG C, under the rotating speed of 200rpm, is led to Cross the rotational shear of screw rod, dispersion makes sodium chloride grind to form crystal grain and be dispersed in formation doping in the tin of semi-molten state Tin;
(2)By step(1)Obtained doped tin is sent into high temperature and pressure homogenizer while hot, and setting temperature is 300-350 DEG C, high Body of calming the anger is nitrogen, and pressure is set as 3MPa, by homogenizer high temperature and pressure, so that doped tin formation injection stream is entered high voltage quiet Electrospun obtains the radial nano wire for Nano grade;
(3)By step(2)Obtained nano wire is sent into two stepwise fluid beds, and the first rank fluidized-bed temperature of setting is in 150- Between 200 DEG C, so that nano wire is quickly aoxidized in complete suspended state lower surface by sufficient air, react 15s, form surface The nano wire of oxidation;Subsequently into second-order fluid bed, setting second-order fluidized-bed temperature is between 800-810 DEG C, by filling The air of foot makes nano wire quickly be aoxidized under complete suspended state, is doped in the sodium chloride crystal grain melting shape of tin with this condition At crystal grain defective hole, while tin is aoxidized, so that tin oxide nano-wire is covered with uniform through hole;
(4)By step(3)Obtained material is cleaned with deionized water, removes remaining sodium chloride, and drying, refinement obtain Fibrous porous oxidation tin negative pole material for lithium battery.
The fibrous porous tin oxide appearance that embodiment 1 obtains is microcosmic such as attached drawing 1 by scanning electron microscopic observation in cotton-shaped For the entangled object of threadiness, fiber is about within 5 μm, and fibre diameter reaches Nano grade.For electrode of lithium cell, battery performance Test result shows that discharge capacity is 725 mAh/g to the electrode material of preparation for the first time, and capacity is 690mAh/g after recycling 300 times, Capacity retention ratio is more than 90%.Therefore, by forming perforation micropore in tin oxide fibre, tin oxide conduct is fundamentally solved The defect of cathode of lithium battery capacity attenuation.
Embodiment 2
(1)By powdered sodium chloride and glass putty with mass ratio 10:200 are uniformly mixed, and are then fed into screw extruder, if The temperature for setting Screw Extrusion press is 220-230 DEG C, makes sodium chloride grind to form crystal grain simultaneously by the rotational shear of screw rod, dispersion It is dispersed in the tin of semi-molten state and forms doped tin;
(2)By step(1)Obtained doped tin is sent into high temperature and pressure homogenizer while hot, and setting temperature is 300-350 DEG C, high Body of calming the anger is nitrogen, and pressure is set as 5MPa by homogenizer high temperature and pressure, so that doped tin formation injection stream is entered high voltage quiet Electrospun obtains the radial nano wire for Nano grade;
(3)By step(2)Obtained nano wire is sent into two stepwise fluid beds, and the first rank fluidized-bed temperature of setting is in 150- Between 200 DEG C, so that nano wire is quickly aoxidized in complete suspended state lower surface by sufficient air, react 10s, form surface The nano wire of oxidation;Subsequently into second-order fluid bed, setting second-order fluidized-bed temperature is between 800-810 DEG C, by filling The air of foot makes nano wire quickly be aoxidized under complete suspended state, is doped in the sodium chloride crystal grain melting shape of tin with this condition At crystal grain defective hole, while tin is aoxidized, so that tin oxide nano-wire is covered with uniform through hole;
(4)By step(3)Obtained material is cleaned with deionized water, removes remaining sodium chloride, and drying, refinement obtain Fibrous porous oxidation tin negative pole material for lithium battery.
The fibrous porous tin oxide that embodiment 2 is obtained is used for electrode of lithium cell, and battery performance test is the results show that system Discharge capacity is 700mAh/g to standby electrode material for the first time, and capacity is 643mAh/g after recycling 300 times.
Embodiment 3
(1)By powdered sodium chloride and glass putty with mass ratio 10:300 are uniformly mixed, and are then fed into twin (double) screw extruder, The temperature that Screw Extrusion press is arranged is 220-230 DEG C, makes sodium chloride grind to form crystal grain by the rotational shear of screw rod, dispersion And it is dispersed in the tin of semi-molten state and forms doped tin;
(2)By step(1)Obtained doped tin is sent into high temperature and pressure homogenizer while hot, and setting temperature is 300-350 DEG C, high Body of calming the anger is nitrogen, by homogenizer high temperature and pressure, so that doped tin is formed injection stream and enters high voltage electrostatic spinning, obtain radial direction For the nano wire of Nano grade;
(3)By step(2)Obtained nano wire is sent into two stepwise fluid beds, and the first rank fluidized-bed temperature of setting is in 150- Between 200 DEG C, so that nano wire is quickly aoxidized in complete suspended state lower surface by sufficient air, react 30s, form surface The nano wire of oxidation;Subsequently into second-order fluid bed, setting second-order fluidized-bed temperature is between 800-810 DEG C, by filling The air of foot makes nano wire quickly be aoxidized under complete suspended state, is doped in the sodium chloride crystal grain melting shape of tin with this condition At crystal grain defective hole, while tin is aoxidized, so that tin oxide nano-wire is covered with uniform through hole;
(4)By step(3)Obtained material is cleaned with deionized water, removes remaining sodium chloride, and drying, refinement obtain Fibrous porous oxidation tin negative pole material for lithium battery.
The fibrous porous tin oxide that embodiment 3 is obtained is used for cathode of lithium battery, with just extremely iron manganese phosphate for lithium material The test battery pack of composition carries out cyclical stability test, and discharge capacity is 720mAh/g for the first time, and capacity is after recycling 300 times 620mAh/g has good cyclical stability.
Embodiment 4
(1)By powdered sodium chloride and glass putty with mass ratio 10:300 are uniformly mixed, and are then fed into conical screw extruding The temperature of machine, setting Screw Extrusion press is 220-230 DEG C, makes sodium chloride grind to be formed by the rotational shear of screw rod, dispersion Crystal grain is simultaneously dispersed in the tin of semi-molten state and forms doped tin;
(2)By step(1)Obtained doped tin is sent into high temperature and pressure homogenizer while hot, and setting temperature is 300-350 DEG C, high Body of calming the anger is nitrogen, and pressure is set as 4MPa by homogenizer high temperature and pressure, so that doped tin formation injection stream is entered high voltage quiet Electrospun obtains the radial nano wire for Nano grade;
(3)By step(2)Obtained nano wire is sent into two stepwise fluid beds, and the first rank fluidized-bed temperature of setting is in 150- Between 200 DEG C, so that nano wire is quickly aoxidized in complete suspended state lower surface by sufficient air, react 20s, form surface The nano wire of oxidation;Subsequently into second-order fluid bed, setting second-order fluidized-bed temperature is between 800-810 DEG C, by filling The air of foot makes nano wire quickly be aoxidized under complete suspended state, is doped in the sodium chloride crystal grain melting shape of tin with this condition At crystal grain defective hole, while tin is aoxidized, so that tin oxide nano-wire is covered with uniform through hole;
(4)By step(3)Obtained material is cleaned with deionized water, removes remaining sodium chloride, and drying, refinement obtain Fibrous porous oxidation tin negative pole material for lithium battery.
The fibrous porous tin oxide that embodiment 4 is obtained is used for cathode of lithium battery, with just extremely iron manganese phosphate for lithium material The test battery pack of composition carries out cyclical stability test, and discharge capacity is 718mAh/g for the first time, and capacity is after recycling 300 times 652mAh/g has good cyclical stability.

Claims (6)

1. a kind of fibrous porous oxidation tin negative pole material for lithium battery, it is characterized in that tin oxide is nano-scale fiber shape, It is covered with uniform through hole on its single fiber, the through hole is for crystal grain defective hole;
Its specific preparation process is as follows:
(1)By powdered sodium chloride and glass putty with mass ratio 10:100-300 is uniformly mixed, and is then fed into screw extruder, if The temperature for setting Screw Extrusion press is 220-230 DEG C, makes sodium chloride grind to form crystal grain simultaneously by the rotational shear of screw rod, dispersion It is dispersed in the tin of semi-molten state and forms doped tin;
(2)By step(1)Obtained doped tin is sent into high temperature and pressure homogenizer while hot, and setting temperature is 300-350 DEG C, high pressure gas Body is nitrogen, by homogenizer high temperature and pressure, so that doped tin is formed injection stream and enters high voltage electrostatic spinning, obtains radial being to receive The other nano wire of meter level;
(3)By step(2)Obtained nano wire is sent into two stepwise fluid beds, and the first rank fluidized-bed temperature of setting is at 150-200 DEG C Between, so that nano wire is quickly aoxidized in complete suspended state lower surface by sufficient air, react 10-30s, forms Surface Oxygen The nano wire of change;Subsequently into second-order fluid bed, setting second-order fluidized-bed temperature passes through abundance between 800-810 DEG C Air so that nano wire is quickly aoxidized under complete suspended state, the sodium chloride crystal grain for being doped in tin with this condition melts to be formed Crystal grain defective hole, while tin is aoxidized, so that tin oxide nano-wire is covered with uniform through hole;
(4)By step(3)Obtained material is cleaned with deionized water, removes remaining sodium chloride, and drying, refinement are used for The fibrous porous oxidation tin negative pole material of lithium battery.
2. a kind of preparation method of fibrous porous oxidation tin negative pole material for lithium battery, specific preparation process are as follows:
(1)By powdered sodium chloride and glass putty with mass ratio 10:100-300 is uniformly mixed, and is then fed into screw extruder, if The temperature for setting Screw Extrusion press is 220-230 DEG C, makes sodium chloride grind to form crystal grain simultaneously by the rotational shear of screw rod, dispersion It is dispersed in the tin of semi-molten state and forms doped tin;
(2)By step(1)Obtained doped tin is sent into high temperature and pressure homogenizer while hot, and setting temperature is 300-350 DEG C, high pressure gas Body is nitrogen, by homogenizer high temperature and pressure, so that doped tin is formed injection stream and enters high voltage electrostatic spinning, obtains radial being to receive The other nano wire of meter level;
(3)By step(2)Obtained nano wire is sent into two stepwise fluid beds, and the first rank fluidized-bed temperature of setting is at 150-200 DEG C Between, so that nano wire is quickly aoxidized in complete suspended state lower surface by sufficient air, react 10-30s, forms Surface Oxygen The nano wire of change;Subsequently into second-order fluid bed, setting second-order fluidized-bed temperature passes through abundance between 800-810 DEG C Air so that nano wire is quickly aoxidized under complete suspended state, the sodium chloride crystal grain for being doped in tin with this condition melts to be formed Crystal grain defective hole, while tin is aoxidized, so that tin oxide nano-wire is covered with uniform through hole;
(4)By step(3)Obtained material is cleaned with deionized water, removes remaining sodium chloride, and drying, refinement are used for The fibrous porous oxidation tin negative pole material of lithium battery.
3. the preparation method of a kind of fibrous porous oxidation tin negative pole material for lithium battery according to claim 2, It is characterized in that:Step(1)The screw extruder is twin (double) screw extruder.
4. the preparation method of a kind of fibrous porous oxidation tin negative pole material for lithium battery according to claim 2, It is characterized in that:Step(1)The screw extruder is parallel dual-screw extruder.
5. the preparation method of a kind of fibrous porous oxidation tin negative pole material for lithium battery according to claim 2, It is characterized in that:Step(2)The pressure of the high temperature and pressure homogenizer is set as 3-5MPa.
6. the preparation method of a kind of fibrous porous oxidation tin negative pole material for lithium battery according to claim 2, It is characterized in that:Step(3)The first rank reaction time be 15s, the reaction time preferably ensures tin surfaces quickly formation compared with Thin stannic oxide layer and be unlikely to nano wire deformation.
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