CN107819116A - A kind of Si conductivity ceramics composite negative pole material and preparation method for lithium battery - Google Patents

A kind of Si conductivity ceramics composite negative pole material and preparation method for lithium battery Download PDF

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CN107819116A
CN107819116A CN201710963680.0A CN201710963680A CN107819116A CN 107819116 A CN107819116 A CN 107819116A CN 201710963680 A CN201710963680 A CN 201710963680A CN 107819116 A CN107819116 A CN 107819116A
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conductivity ceramics
silicon
negative pole
lithium battery
composite negative
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CN107819116B (en
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陈庆
廖健淞
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Jiangsu Baker New Material Co., Ltd.
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Chengdu New Keli Chemical Science 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
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • 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
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/386—Silicon or alloys based on silicon
    • 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
    • H01M4/485—Selection 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
    • 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
    • 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
    • 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 invention provides a kind of Si conductivity ceramics composite negative pole material and preparation method for lithium battery, it is characterised in that suppresses Volume Changes of the silicium cathode material in discharge and recharge using conductivity ceramics as skeleton.It is distributed to form secondary granule with conductivity ceramics after silicon nanoparticle passivation, alleviates size of the volumetric expansion of silicon materials without changing secondary granule；For conductivity ceramics as skeleton, silicon nano is all electro-chemical activity, therefore with more preferably specific capacity；Conductivity ceramics has preferable mechanical performance, can absorb by the bulk effect of silicon and caused internal stress.Further, carbon coating layer reduces the activity of nano surface material, improves solid electrolyte interface film, and electrode is integrated and electrical conductivity from electrolyte corrosion, when keeping Volume Changes for protection activity material, therefore improves electrical conductivity, electron mobility and cyclical stability.

Description

A kind of Si- conductivity ceramics composite negative pole material and preparation method for lithium battery
Technical field
The present invention relates to the preparing technical field of electrode material, more particularly to a kind of conductive potteries of Si- for lithium battery Porcelain composite negative pole material and preparation method.
Background technology
With the extensive use and fast development of various portable electric appts and electric automobile, its dynamical system is changed Learn demand and the performance requirement sharp increase of power supply, lithium ion battery is so that it is bigger than energy, operating voltage is high, self-discharge rate is small etc. Advantage is widely used in mobile electronic terminal device field, and with the growth to high capacity power source demand so that lithium-ion electric Pond is developed towards the direction of higher energy density.The lithium ion battery of commercialization at present uses cobalt acid lithium/graphite system mostly, by In relatively low theoretical capacity of the system electrode itself, by improve battery preparation technique improve battery performance be difficult to obtain it is prominent Broken property progress.In general, total specific capacity of lithium ion battery be by the specific capacity of positive electrode, the specific capacity of negative material and What other components of battery determined, the specific capacity of wherein positive and negative electrode material is to improve the key of the total specific capacity of lithium ion battery.Cause This, the great urgency of exploitation of the lithium ion battery electrode material of Novel high-specific capacity flexible.
Nano-silicon, refer to that diameter is less than 5 nanometers of crystal silicon particle, be a kind of important nonmetallic amorphous materials. Nano silica fume has the characteristics that purity is high, particle diameter is small, is evenly distributed, specific surface area is big, high surface, apparent density are low, and It is nontoxic, tasteless.The application field of nano-silicon is extensive：（1）Si-C composite material is formed with graphite material, as lithium ion battery Negative material, greatly improve the capacity of lithium ion battery；（2）For manufacturing high-temperaure coating and refractory material.
In recent years, the material of lithium battery silicium cathode material is increasingly becoming a big focus.Lithium of the silicium cathode as a new generation Ion battery cathode material, its capacity reach as high as 4200mAh/g, are more than 10 times of graphite cathode material, are most to wish Lithium ion battery negative material of future generation.But shortcoming is also clearly when silicon is as lithium ion battery negative material.First, silicon It is semi-conducting material, the electrical conductivity of itself is relatively low；Secondly, in electrochemistry cyclic process, the insertion and abjection of lithium ion can make More than 300% expansion and contraction occurs for silica-base material volume, and resulting mechanicals efforts can make the gradual powder of silica-base material Change, cause structure collapses, ultimately result in electrode active material and depart from collector, lose electrical contact, and then cause lithium-ion electric The cycle performance in pond substantially reduces.Further, since this bulk effect, silica-base material is difficult to form stable consolidate in the electrolytic solution Body electrolyte interface film, caving in and destroy along with electrode structure, the silicon face exposed can constantly form new solid electricity Matter interfacial film is solved, is further exacerbated by the corrosion of silicon and the decay of capacity of lithium ion battery.
To improve silicon-based anode cycle performance, structural stability of the material in cyclic process is improved, generally by silicon materials Nanosizing and Composite.At present, the main direction of studying of silicon materials nanosizing includes：Nano silicon particles（Zero-dimension nano）, silicon Nano wire/pipe（1-dimention nano）, silicon thin film（Two-dimensional nano）With 3D loose structures silicon, hollow porous silicon（Three-dimensional manometer Change）；The main direction of studying of silicon materials Composite includes：Silicon/metal mold is compound, silicon/carbon type is compound and ternary form is compound（Such as Silicon/unformed carbon graphite three-component compound system）.But still it is difficult to the volumetric expansion of effectively buffering silicon so that silicon is in lithium battery Negative pole is hindered in utilizing.
The content of the invention
To overcome the defects of volumetric expansion failure easily occurs for silicium cathode in lithium battery, the invention provides one kind to be used for lithium electricity The Si- conductivity ceramics composite negative pole materials in pond, using conductivity ceramics as skeleton, two level is distributed in after silicon nanoparticle is passivated In the interior void of grain, size of the volumetric expansion of silicon materials without changing secondary granule is alleviated, and nano-silicon is all electrification Activity is learned, therefore with more preferably specific capacity.The present invention by metal oxide to improve the electrical conductivity of secondary granule, effectively Promote electron transfer and improve cycle life, while whole secondary particle is covered using carbon coating layer, protection activity material from Electrolyte corrosion, and improve the rate stability and cyclical stability of Si- conductivity ceramics negative materials.
Concrete technical scheme of the present invention is as follows：
The preparation method of a kind of Si- conductivity ceramics composite negative pole materials for lithium battery, it is characterised in that use conductivity ceramics Suppress Volume Changes of the silicium cathode material in discharge and recharge as skeleton, using silica and conductivity ceramics as raw material, pass through reduction After silica uniformly mixes with conductivity ceramics slurry, sintered under high temperature inert atmosphere and Si- conductivity ceramics composite negative poles are made Material；Specifically preparation process is：
（1）Reduction is heated after a certain proportion of coke is uniformly mixed with silicon oxide powder and obtains thick silicon, after being fully ground refinement Chlorine heating response generation silicon tetrachloride is passed through, is heated again after cooling and is passed through hydrogen reducing silicon tetrachloride and obtain elemental silicon Nano particle presoma, passivation nano silicon particles of the average grain diameter less than 5nm are obtained using passivator processing presoma；
（2）By step（1）The passivation nano silicon particles and trace meter oxide, conductivity ceramics slurry of acquisition are in certain proportion Mixing, stirs, further improves dispersivity by vibration of ultrasonic wave, finally under vacuum heating conditions, using atomizer Scattered slurry spray is granulated to form microballoon；
（3）By step（2）The microballoon of acquisition is fitted into chemical vapor deposition unit, after being warming up to certain temperature under an inert atmosphere Insulation, while propylene, acetylene combination gas are passed through, the pyrolytic carbon layer to form densification is deposited in microsphere surface, finally in indifferent gas Heat-agglomerating under atmosphere and obtain the Si- conductivity ceramics composite negative pole materials of carbon coating.
Preferably, step（1）Described silicon oxide powder and the rate of charge of coke are 1:1.5~1:2, heat reduction temperature For 2800 ~ 2900 DEG C.
Preferably, step（1）The described heating response temperature being passed through after chlorine is 480 ~ 500 DEG C；Described is passed through hydrogen The heating response temperature of gas is 1100 ~ 1150 DEG C.
Preferably, step（1）Described passivator is nafoxidine, N,N-dimethylformamide, 1-METHYLPYRROLIDONE In any one.
Preferably, step（2）The solid-phase component of described conductivity ceramics slurry by mass percentage, by 30 ~ 35% Al Powder, 30 ~ 35% Ti powder and 30 ~ 35% TiN powder are formed；The trace meter oxide is CuO or NiO, dosage For the 0.5 ~ 1% of conductivity ceramics slurry solid-phase component quality；Described passivation nano silicon particles and conductivity ceramics slurry solid-phase component Weight ratio be 0.2 ~ 0.3.
Preferably, step（2）The frequency of described ultrasonic vibration is 40 ~ 45kHz, and jitter time is 10 ~ 15 minutes；It is described Mist projection granulating when heating in vacuum temperature be 160 ~ 180 DEG C.
Preferably, step（3）Described inert atmosphere is nitrogen, argon gas is formed with arbitrary proportion；Described propylene, acetylene It is 1 to combine both mol ratios in gas:2.5~3.
Preferably, step（3）Described heating and thermal insulation temperature is 380 ~ 410 DEG C；
Preferably, step（3）Described heat-agglomerating temperature is 1380 ~ 1450 DEG C, and sintering time is 20 ~ 30min.
A kind of Si- conductivity ceramics composite negative pole materials for lithium battery, it is characterized in that being prepared by the above method.It is logical Bulk effect problem can effectively be alleviated by crossing the nanosizing of silicon, while also improve the diffusion velocity of lithium ion, so as to improve material Chemical property.The present invention by being introduced into silicon materials there are very good mechanical properties mutually to be led with the second of certain electric conductivity Electroceramics, conductivity ceramics have preferable mechanical performance, can absorb by the bulk effect of silicon and caused internal stress.Silicon is Semi-conducting material, its electric conductivity is poor, and the present invention improves the conductance of Si- conductivity ceramics composites by carbon integument Rate, electron mobility and electrochemical stability, meanwhile, carbon coating layer can also reduce the activity of nano surface material, improve solid- Electrolyte interface film, electrode is integrated and electrical conductivity from electrolyte corrosion, when keeping Volume Changes for protection activity material, therefore carries High rate stability and cyclical stability.Wherein the selection of passivator has considerable influence to the microscopic appearance of resulting materials, Obtained from nano-silicon chemical property it is also entirely different, when with nafoxidine, DMF, N- methylpyrroles When any one in alkanone is passivator, gained nano silicon particles show uniform spherical, and discharge capacity is high first, repeatedly Decay after circulation small.In order to ensure that slurry has a preferable mobility and optimal mist projection granulating effect, conductivity ceramics slurry kind water with The weight ratio of solid-phase component should be controlled 0.32 ~ 0.40 or so.
It is and existing the invention provides a kind of Si- conductivity ceramics composite negative pole material and preparation method for lithium battery The characteristics of technology is compared, and it is protruded and excellent effect are：
（1）The present invention is distributed in the interior void of secondary granule after silicon nanoparticle passivation, delayed using conductivity ceramics as skeleton Size of the volumetric expansion of silicon materials without changing secondary granule is solved；
（2）In the technical program, for conductivity ceramics as skeleton, silicon nano is all electro-chemical activity, therefore with more preferably Specific capacity；
（3）Blended metal oxide of the present invention effectively facilitates electron transfer and improved and circulate to improve the electrical conductivity of secondary granule Life-span；
（4）The carbon coating layer of the present invention covers whole secondary particle, and protection activity material improves from electrolyte corrosion The rate stability and cyclical stability of Si- conductivity ceramics negative materials；
Embodiment
Below by way of embodiment, the present invention is described in further detail, but this should not be interpreted as to the model of the present invention Enclose and be only limitted to following example.In the case where not departing from above method thought of the present invention, according to ordinary skill knowledge The various replacements or change made with customary means, should be included in the scope of the present invention.
Embodiment 1
A kind of Si- conductivity ceramics composite negative pole materials for lithium battery, it is as follows that it prepares the step of electricity：
Certain 9.6kg coke is uniformly mixed with 6.4kg SiO 2 powders, airtight heating is reduced to obtain slightly to 2800 DEG C Silicon；Obtained thick silicon is carried out being passed through chlorine after being fully ground refinement and is heated to 485 DEG C of reaction lifes until silicon grain turns completely Silicon tetrachloride is melted into, hydrogen is passed through after Slow cooling and then is heated to 1100 DEG C of reduction silicon tetrachlorides obtains receiving for elemental silicon Rice grain presoma；Passivation silicon nanometer of the average grain diameter less than 5nm is obtained using 1-METHYLPYRROLIDONE immersion treatment presoma Particle；Passivation nano silicon particles are mixed and stirred for uniformly with conductivity ceramics slurry, wherein, passivation nano silicon particles are made pottery with conductive The weight ratio of porcelain slurry solid-phase component is 0.2.The solid-phase component of conductivity ceramics slurry by mass percentage, by 30% Al powder End, 35% Ti powder and 35% TiN powder are formed.And nickel oxide is added, dosage is conductivity ceramics slurry solid-phase component matter The 0.51% of amount.；It is true by one by 10 minutes dispersivitys for further improving mixed slurry of vibration of ultrasonic wave that frequency is 40kHz Empty spray chamber is heated to 170 DEG C, is granulated to form microballoon by scattered slurry spray using atomizer；By the microballoon obtained of spraying It is fitted into chemical vapor deposition unit, in N2It is incubated, is passed through by propylene, acetylene molar ratio after 400 DEG C are warming up under inert atmosphere For 1:2.5 mixed gas formed, the pyrolytic carbon layer to form densification is deposited in microsphere surface；Finally, in N2Under inert atmosphere It is heated to 1400 DEG C and insulation sinters and obtain the secondary granule of carbon coating for 20 minutes, as Si- conductivity ceramics composite negative pole material Material.
By sample preparation into negative electrode material, positive pole lithium nickel mangaic acid aluminium is matched, is prepared into the box hat battery of 3Ah specifications, Under the test condition that 1C chargings, 10C discharge, circulate 500 weeks, the obtained internal resistance of cell, monomer capacity, the capacity after 500 weeks Conservation rate and charging interval and data are as shown in table 1.It can be seen that pass through lithium battery prepared by embodiment 1 and graphite cathode material lithium Battery is compared, and is obviously improved in the performances such as internal resistance, monomer capacity, cycle-index and quick charge.
Embodiment 2
A kind of Si- conductivity ceramics composite negative pole materials for lithium battery, it is as follows that it prepares the step of electricity：
Certain 12kg coke is uniformly mixed with 7.4kg SiO 2 powders, airtight heating is reduced to obtain slightly to 2900 DEG C Silicon；Obtained thick silicon is carried out being passed through chlorine after being fully ground refinement and is heated to 495 DEG C of reaction lifes until silicon grain turns completely Silicon tetrachloride is melted into, hydrogen is passed through after Slow cooling and then is heated to 1150 DEG C of reduction silicon tetrachlorides obtains receiving for elemental silicon Rice grain presoma；Passivation nano silicon particles of the average grain diameter less than 5nm are obtained using nafoxidine processing presoma；It will obtain Passivation nano silicon particles and 15kg conductivity ceramics slurries be mixed and stirred for uniformly, wherein, conductivity ceramics slurry contains 3.75kg Aluminium powder, 3.3kg titanium valves and 3.85kg nitridation titanium valves are simultaneously configured to conductivity ceramics slurry with 4L water；Add 0.11kg cupric oxide；It is logical 10 minutes dispersivitys for further improving mixed slurry of the vibration of ultrasonic wave that overfrequency is 50kHz, a vacuum spraying room is heated To 160 DEG C, scattered slurry spray is granulated to form microballoon using atomizer；By the microballoon loading chemical gaseous phase obtained of spraying In precipitation equipment, it is incubated, is passed through by propylene, acetylene molar ratio 1 after being warming up to 390 DEG C under an argon atmosphere:3 formed it is mixed Gas is closed, the pyrolytic carbon layer to form densification is deposited in microsphere surface；Finally, 1400 DEG C are heated under argon inert atmosphere and is protected Temperature sinters and obtains the secondary granule of carbon coating for 30 minutes, as Si- conductivity ceramics composite negative pole material.
By sample preparation into negative electrode material, positive pole lithium nickel mangaic acid aluminium is matched, is prepared into the box hat battery of 3Ah specifications, Under the test condition that 1C chargings, 10C discharge, circulate 500 weeks, the obtained internal resistance of cell, monomer capacity, the capacity after 500 weeks Conservation rate and charging interval and data are as shown in table 1.It can be seen that pass through lithium battery prepared by embodiment 2 and graphite cathode material lithium Battery is compared, and is obviously improved in the performances such as internal resistance, monomer capacity, cycle-index and quick charge.
Embodiment 3
A kind of Si- conductivity ceramics composite negative pole materials for lithium battery, it is as follows that it prepares the step of electricity：
Certain 10kg coke is uniformly mixed with 6.4kg SiO 2 powders, airtight heating is reduced to obtain slightly to 2850 DEG C Silicon；Obtained thick silicon is carried out being passed through chlorine after being fully ground refinement and is heated to 485 DEG C of reaction lifes until silicon grain turns completely Silicon tetrachloride is melted into, hydrogen is passed through after Slow cooling and then is heated to 1120 DEG C of reduction silicon tetrachlorides obtains receiving for elemental silicon Rice grain presoma；Passivation nano silicon particles of the average grain diameter less than 5nm are obtained using 1-METHYLPYRROLIDONE processing presoma； The passivation nano silicon particles of acquisition and 16.5kg conductivity ceramics slurries are mixed and stirred for uniformly, wherein, conductivity ceramics slurry contains There are 4.2kg aluminium powders, 4.14kg titanium valves and 3.6kg nitridation titanium valves and conductivity ceramics slurry is configured to 4.5L water；Add 0.06kg Nickel oxide, by 13 minutes dispersivitys for further improving mixed slurry of vibration of ultrasonic wave that frequency is 41kHz, a vacuum is sprayed Fog chamber is heated to 170 DEG C, is granulated to form microballoon by scattered slurry spray using atomizer；By the microballoon loading obtained of spraying In chemical vapor deposition unit, in N2It is incubated, is passed through by propylene, acetylene molar ratio 1 after 385 DEG C are warming up under inert atmosphere: 2.6 mixed gas formed, the pyrolytic carbon layer to form densification is deposited in microsphere surface；Finally, in N2Heated under inert atmosphere To 1450 DEG C and insulation sinters and obtains the secondary granule of carbon coating for 25 minutes, as Si- conductivity ceramics composite negative pole material.
By sample preparation into negative electrode material, positive pole lithium nickel mangaic acid aluminium is matched, is prepared into the box hat battery of 3Ah specifications, Under the test condition that 1C chargings, 10C discharge, circulate 500 weeks, the obtained internal resistance of cell, monomer capacity, the capacity after 500 weeks Conservation rate and charging interval and data are as shown in table 1.It can be seen that pass through lithium battery prepared by embodiment 3 and graphite cathode material lithium Battery is compared, and is obviously improved in the performances such as internal resistance, monomer capacity, cycle-index and quick charge.
Embodiment 4
A kind of Si- conductivity ceramics composite negative pole materials for lithium battery, it is as follows that it prepares the step of electricity：
Certain 9kg coke is uniformly mixed with 4.7kg silicon monoxides powder, airtight heating is reduced to obtain slightly to 2860 DEG C Silicon；Obtained thick silicon is carried out being passed through chlorine after being fully ground refinement and is heated to 495 DEG C of reaction lifes until silicon grain turns completely Silicon tetrachloride is melted into, hydrogen is passed through after Slow cooling and then is heated to 1130 DEG C of reduction silicon tetrachlorides obtains receiving for elemental silicon Rice grain presoma；Passivation silicon nanometer of the average grain diameter less than 5nm is obtained using N,N-dimethylformamide processing presoma Grain；The passivation nano silicon particles of acquisition and 18kg conductivity ceramics slurries are mixed and stirred for uniformly, wherein, conductivity ceramics slurry contains There are 4.55kg aluminium powders, 3.9kg titanium valves and 4.42kg nitridation titanium valves and conductivity ceramics slurry is configured to 5L water；Add 0.13kg oxygen Change nickel, by 15 minutes dispersivitys for further improving mixed slurry of vibration of ultrasonic wave that frequency is 50kHz, by a vacuum spraying Room is heated to 180 DEG C, is granulated to form microballoon by scattered slurry spray using atomizer；By the microballoon loadingization obtained of spraying Learn in vapor phase growing apparatus, in N2It is incubated, is passed through by propylene, acetylene molar ratio 1 after 400 DEG C are warming up under inert atmosphere:3 institutes The mixed gas of composition, the pyrolytic carbon layer to form densification is deposited in microsphere surface；Finally, in N21430 are heated under inert atmosphere DEG C and be incubated and sinter and obtain the secondary granule of carbon coating for 20 minutes, as Si- conductivity ceramics composite negative pole material.
By sample preparation into negative electrode material, positive pole lithium nickel mangaic acid aluminium is matched, is prepared into the box hat battery of 3Ah specifications, Under the test condition that 1C chargings, 10C discharge, circulate 500 weeks, the obtained internal resistance of cell, monomer capacity, the capacity after 500 weeks Conservation rate and charging interval and data are as shown in table 1.It can be seen that pass through lithium battery prepared by embodiment 4 and graphite cathode material lithium Battery is compared, and is obviously improved in the performances such as internal resistance, monomer capacity, cycle-index and quick charge.
Embodiment 5
A kind of Si- conductivity ceramics composite negative pole materials for lithium battery, it is as follows that it prepares the step of electricity：
Certain 8kg coke is uniformly mixed with 4.7kg silicon monoxides powder, airtight heating is reduced to obtain slightly to 2880 DEG C Silicon；Obtained thick silicon is carried out being passed through chlorine after being fully ground refinement and is heated to 500 DEG C of reaction lifes until silicon grain turns completely Silicon tetrachloride is melted into, hydrogen is passed through after Slow cooling and then is heated to 1140 DEG C of reduction silicon tetrachlorides obtains receiving for elemental silicon Rice grain presoma；Passivation nano silicon particles of the average grain diameter less than 5nm are obtained using 1-METHYLPYRROLIDONE processing presoma； The passivation nano silicon particles of acquisition and 19kg conductivity ceramics slurries are mixed and stirred for uniformly, wherein, conductivity ceramics slurry contains 4.9kg aluminium powders, 4.2kg titanium valves and 4.83kg nitridation titanium valves are simultaneously configured to conductivity ceramics slurry with 5L water；Add 0.07kg oxidations Nickel, by 12 minutes dispersivitys for further improving mixed slurry of vibration of ultrasonic wave that frequency is 48kHz, by a vacuum spraying room 175 DEG C are heated to, is granulated to form microballoon by scattered slurry spray using atomizer；By the microballoon loading chemistry obtained of spraying In vapor phase growing apparatus, in N2It is incubated, is passed through by propylene, acetylene molar ratio 1 after 405 DEG C are warming up under inert atmosphere:2.9 institute The mixed gas of composition, the pyrolytic carbon layer to form densification is deposited in microsphere surface；Finally, in N21420 are heated under inert atmosphere DEG C and be incubated and sinter and obtain the secondary granule of carbon coating for 22 minutes, as Si- conductivity ceramics composite negative pole material.
By sample preparation into negative electrode material, positive pole lithium nickel mangaic acid aluminium is matched, is prepared into the box hat battery of 3Ah specifications, Under the test condition that 1C chargings, 10C discharge, circulate 500 weeks, the obtained internal resistance of cell, monomer capacity, the capacity after 500 weeks Conservation rate and charging interval and data are as shown in table 1.It can be seen that pass through lithium battery prepared by embodiment 5 and graphite cathode material lithium Battery is compared, and is obviously improved in the performances such as internal resistance, monomer capacity, cycle-index and quick charge.
Comparative example 1
A kind of Si- conductivity ceramics composite negative pole materials for lithium battery, it is as follows that it prepares the step of electricity：
Certain 8kg coke is uniformly mixed with 4.7kg silicon monoxides powder, airtight heating is reduced to obtain slightly to 2880 DEG C Silicon；Obtained thick silicon is carried out being passed through chlorine after being fully ground refinement and is heated to 500 DEG C of reaction lifes until silicon grain turns completely Silicon tetrachloride is melted into, hydrogen is passed through after Slow cooling and then is heated to 1140 DEG C of reduction silicon tetrachlorides obtains receiving for elemental silicon Rice grain presoma；The nano particle presoma of elemental silicon and 19kg conductivity ceramics slurries are mixed and stirred for uniformly, wherein, lead Electroceramics slurry contains 4.9kg aluminium powders, 4.2kg titanium valves and 4.83kg nitridation titanium valves and is configured to conductivity ceramics slurry with 5L water； 0.07kg nickel oxide is added, 12 minutes dispersivitys for further improving mixed slurry of vibration of ultrasonic wave by frequency for 48kHz, One vacuum spraying room is heated to 175 DEG C, is granulated to form microballoon by scattered slurry spray using atomizer；Spraying is obtained Microballoon be fitted into chemical vapor deposition unit, in N2It is incubated, is passed through by propylene, acetylene after 405 DEG C are warming up under inert atmosphere Mol ratio is 1:2.9 mixed gas formed, the pyrolytic carbon layer to form densification is deposited in microsphere surface；Finally, in N2Inertia 1420 DEG C are heated under atmosphere and insulation sinters and obtain the secondary granule of carbon coating for 22 minutes, as Si- conductivity ceramics is compound Negative material.
By sample preparation into negative electrode material, positive pole lithium nickel mangaic acid aluminium is matched, is prepared into the box hat battery of 3Ah specifications, Under the test condition that 1C chargings, 10C discharge, circulate 500 weeks, the obtained internal resistance of cell, monomer capacity, the capacity after 500 weeks Conservation rate and charging interval and data are as shown in table 1.
Comparative example 2
Certain 8kg coke is uniformly mixed with 4.7kg silicon monoxides powder, airtight heating is reduced to obtain slightly to 2880 DEG C Silicon；Obtained thick silicon is carried out being passed through chlorine after being fully ground refinement and is heated to 500 DEG C of reaction lifes until silicon grain turns completely Silicon tetrachloride is melted into, hydrogen is passed through after Slow cooling and then is heated to 1140 DEG C of reduction silicon tetrachlorides obtains receiving for elemental silicon Rice grain presoma；Passivation nano silicon particles of the average grain diameter less than 5nm are obtained using 1-METHYLPYRROLIDONE processing presoma； The passivation nano silicon particles of acquisition are fitted into chemical vapor deposition unit, in N2It is incubated after 405 DEG C are warming up under inert atmosphere, It is passed through by propylene, acetylene molar ratio 1:2.9 mixed gas formed, the pyrolytic carbon to form densification is deposited in microsphere surface Layer；Finally, in N21420 DEG C are heated under inert atmosphere and insulation sinters and obtain the secondary granule of carbon coating for 22 minutes, is Si composite negative pole materials.
By sample preparation into negative electrode material, positive pole lithium nickel mangaic acid aluminium is matched, is prepared into the box hat battery of 3Ah specifications, Under the test condition that 1C chargings, 10C discharge, circulate 500 weeks, the obtained internal resistance of cell, monomer capacity, the capacity after 500 weeks Conservation rate and charging interval and data are as shown in table 1.
Comparative example 3
A kind of Si- conductivity ceramics composite negative pole materials for lithium battery, it is as follows that it prepares the step of electricity：
Certain 8kg coke is uniformly mixed with 4.7kg silicon monoxides powder, airtight heating is reduced to obtain slightly to 2880 DEG C Silicon；Obtained thick silicon is carried out being passed through chlorine after being fully ground refinement and is heated to 500 DEG C of reaction lifes until silicon grain turns completely Silicon tetrachloride is melted into, hydrogen is passed through after Slow cooling and then is heated to 1140 DEG C of reduction silicon tetrachlorides obtains receiving for elemental silicon Rice grain presoma；Passivation nano silicon particles of the average grain diameter less than 5nm are obtained using 1-METHYLPYRROLIDONE processing presoma； The passivation nano silicon particles of acquisition and 19kg conductivity ceramics slurries are mixed and stirred for uniformly, wherein, conductivity ceramics slurry contains 4.9kg aluminium powders, 4.2kg titanium valves and 4.83kg nitridation titanium valves are simultaneously configured to conductivity ceramics slurry with 5L water；Add 0.07kg oxidations Nickel, by 12 minutes dispersivitys for further improving mixed slurry of vibration of ultrasonic wave that frequency is 48kHz, by a vacuum spraying room 175 DEG C are heated to, is granulated to form microballoon by scattered slurry spray using atomizer；In N21420 are heated under inert atmosphere DEG C and be incubated and sinter and obtain the secondary granule of carbon coating for 22 minutes, as Si- conductivity ceramics composite negative pole material.
By sample preparation into negative electrode material, positive pole lithium nickel mangaic acid aluminium is matched, is prepared into the box hat battery of 3Ah specifications, Under the test condition that 1C chargings, 10C discharge, circulate 500 weeks, the obtained internal resistance of cell, monomer capacity, the capacity after 500 weeks Conservation rate and charging interval and data are as shown in table 1.
Table 1

Claims (9)

1. the preparation method of a kind of Si- conductivity ceramics composite negative pole materials for lithium battery, it is characterised in that use conductive pottery Porcelain suppresses Volume Changes of the silicium cathode material in discharge and recharge as skeleton, using silica and conductivity ceramics as raw material, by also After former silica uniformly mixes with conductivity ceramics slurry, sintered under high temperature inert atmosphere and Si- conductivity ceramics Compound Negatives are made Pole material；Specifically preparation process is：
（1）Reduction is heated after a certain proportion of coke is uniformly mixed with silicon oxide powder and obtains thick silicon, after being fully ground refinement Chlorine heating response generation silicon tetrachloride is passed through, is heated again after cooling and is passed through hydrogen reducing silicon tetrachloride and obtain elemental silicon Nano particle presoma, passivation nano silicon particles of the average grain diameter less than 5nm are obtained using passivator processing presoma；
（2）By step（1）The passivation nano silicon particles and trace meter oxide, conductivity ceramics slurry of acquisition are in certain proportion Mixing, stirs, further improves dispersivity by vibration of ultrasonic wave, finally under vacuum heating conditions, using atomizer Scattered slurry spray is granulated to form microballoon；
（3）By step（2）The microballoon of acquisition is fitted into chemical vapor deposition unit, after being warming up to certain temperature under an inert atmosphere Insulation, while propylene, acetylene combination gas are passed through, the pyrolytic carbon layer to form densification is deposited in microsphere surface, finally in indifferent gas Heat-agglomerating under atmosphere and obtain the Si- conductivity ceramics composite negative pole materials of carbon coating.
2. the preparation method of a kind of Si- conductivity ceramics composite negative pole materials for lithium battery according to claim 1, it is special Sign is：Step（1）Described silicon oxide powder and the rate of charge of coke are 1:1.5~1:2, heating reduction temperature be 2800 ~ 2900℃。
3. the preparation method of a kind of Si- conductivity ceramics composite negative pole materials for lithium battery according to claim 1, it is special Sign is：Step（1）The described heating response temperature being passed through after chlorine is 480 ~ 500 DEG C；The described heating for being passed through hydrogen Reaction temperature is 1100 ~ 1150 DEG C.
4. the preparation method of a kind of Si- conductivity ceramics composite negative pole materials for lithium battery according to claim 1, it is special Sign is：Step（1）Described passivator is any in nafoxidine, N,N-dimethylformamide, 1-METHYLPYRROLIDONE It is a kind of.
5. the preparation method of a kind of Si- conductivity ceramics composite negative pole materials for lithium battery according to claim 1, it is special Sign is：Step（2）The solid-phase component of described conductivity ceramics slurry by mass percentage, by 30 ~ 35% Al powder, 30 ~ 35% Ti powder and 30 ~ 35% TiN powder are formed；The trace meter oxide is CuO or NiO, and dosage is made pottery to be conductive The 0.5 ~ 1% of porcelain slurry solid-phase component quality；The weight ratio of described passivation nano silicon particles and conductivity ceramics slurry solid-phase component For 0.2 ~ 0.3.
6. the preparation method of a kind of Si- conductivity ceramics composite negative pole materials for lithium battery according to claim 1, it is special Sign is：Step（2）The frequency of described ultrasonic vibration is 40 ~ 45kHz, and jitter time is 10 ~ 15 minutes；Described spraying is made Heating in vacuum temperature during grain is 160 ~ 180 DEG C.
7. the preparation method of a kind of Si- conductivity ceramics composite negative pole materials for lithium battery according to claim 1, it is special Sign is：Step（3）Described inert atmosphere is nitrogen, argon gas is formed with arbitrary proportion；Described propylene, acetylene combination gas In both mol ratio be 1:2.5~3.
8. the preparation method of a kind of Si- conductivity ceramics composite negative pole materials for lithium battery according to claim 1, it is special Sign is：Step（3）Described heating and thermal insulation temperature is 380 ~ 410 DEG C；Described heat-agglomerating temperature is 1380 ~ 1450 DEG C, Sintering time is 20 ~ 30min.
9. a kind of Si- conductivity ceramics composite negative pole materials for lithium battery, it is characterised in that by any one of claim 1-8 institutes The method stated is prepared.
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CN112952071A (en) * 2021-04-08 2021-06-11 合肥国轩高科动力能源有限公司 Porous conductive ceramic composite silicon negative electrode material and preparation method thereof
CN115084530A (en) * 2022-08-19 2022-09-20 溧阳天目先导电池材料科技有限公司 High-cycle silicon-based negative electrode material and preparation method and application thereof
CN115117327A (en) * 2022-08-25 2022-09-27 溧阳天目先导电池材料科技有限公司 Low-expansion silicon-based composite material and preparation method and application thereof
WO2023039750A1 (en) * 2021-09-15 2023-03-23 宁德新能源科技有限公司 Negative electrode composite material and use thereof

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112952071A (en) * 2021-04-08 2021-06-11 合肥国轩高科动力能源有限公司 Porous conductive ceramic composite silicon negative electrode material and preparation method thereof
CN112952071B (en) * 2021-04-08 2022-03-18 合肥国轩高科动力能源有限公司 Porous conductive ceramic composite silicon negative electrode material and preparation method thereof
WO2023039750A1 (en) * 2021-09-15 2023-03-23 宁德新能源科技有限公司 Negative electrode composite material and use thereof
CN115084530A (en) * 2022-08-19 2022-09-20 溧阳天目先导电池材料科技有限公司 High-cycle silicon-based negative electrode material and preparation method and application thereof
CN115117327A (en) * 2022-08-25 2022-09-27 溧阳天目先导电池材料科技有限公司 Low-expansion silicon-based composite material and preparation method and application thereof

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