CN104269521B - Carbon/silicon/blocky graphite cathode material for lithium ion battery, preparation method and lithium ion battery - Google Patents

Carbon/silicon/blocky graphite cathode material for lithium ion battery, preparation method and lithium ion battery Download PDF

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CN104269521B
CN104269521B CN201410556823.2A CN201410556823A CN104269521B CN 104269521 B CN104269521 B CN 104269521B CN 201410556823 A CN201410556823 A CN 201410556823A CN 104269521 B CN104269521 B CN 104269521B
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silicon
blocky graphite
carbon
lithium ion
ion battery
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CN104269521A (en
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徐军红
陈玉
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LUOYANG YUEXING NEW ENERGY TECHNOLOGY CO LTD
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LUOYANG YUEXING NEW ENERGY TECHNOLOGY 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/134—Electrodes based on metals, Si or alloys
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
    • 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 discloses a carbon/silicon/blocky graphite cathode material for a lithium ion battery, a preparation method and the lithium ion battery. The cathode material comprises a silicon/blocky graphite composite base body, wherein a carbon layer is wrapped on the surface of the silicon/blocky graphite composite base body; the silicon/blocky graphite composite base body comprises blocky graphite particles filled with silicon powder in surface pores. According to the carbon/silicon/blocky graphite cathode material for the lithium ion battery disclosed by the invention, on the basis of improving the capacity of the cathode material by utilizing the silicon powder, the reversible capacity of the carbon-based material is improved, huge volume change of the silicon particles generated in the charging and discharge process is effectively buffered, and the volume expansion of silicon is restricted; the obtained carbon/silicon/blocky graphite cathode material has the characteristics of high tap density, high reversible capacity, designable capacity and stable cycle performance, and thus the electrochemical performance of the lithium ion battery is improved, the cycle stability of the lithium ion battery is improved, the service life of the lithium ion battery is prolonged, and the requirement on high energy density of lithium ion batteries in the market is met.

Description

A kind of lithium ion battery carbon/silicon/blocky graphite negative material, preparation method and lithium Ion battery
Technical field
The invention belongs to technical field of lithium ion is and in particular to a kind of lithium ion battery carbon/silicon/blocky graphite is born Pole material, also relates to a kind of preparation method of lithium ion battery carbon/silicon/blocky graphite negative material and adopts this negative pole The lithium ion battery of material.
Background technology
Lithium ion battery becomes storage because having the advantages such as operating voltage is high, specific energy is high, electric discharge is steady, have extended cycle life Outshining othersOne branch of the tree is particularly thriving of energy field, has been widely used in the fields such as portable electric appts, electric tool, Aero-Space.Negative pole material Material enjoys people to pay close attention to as lithium ion battery critical material always.At present, although business-like graphite negative electrodes material is electrochemical Learn function admirable, safe and reliable, but its theoretical specific capacity is only 372mAh/g it is impossible to meet people to high-energy-density, high power The demand of rate performance lithium ion battery.For adapting to the demand in high power capacity, high-multiplying-power battery market, people start to try to explore and open Send out novel anode material.
Silicon materials attract the eyeball of people with the ultra-high capacity of its 4200mAh/g, its rich reserves, environmentally friendly. However, silicon as during lithium ion battery negative material exist a fatal problem, that is, battery in charge and discharge process be accompanied by huge Big Volume Changes (＞ 300%), after the embedding de- lithium of being repeated several times property, material occurs crackle, or even powder of detached, leads to Cycle performance fails, electrode failure.
At present, be commonly used to improve silicium cathode material circulation performance method mainly have silicon grain nanosizing, silicon and inertia or Active material be combined etc., wherein silicon/carbon composite is the most considerable.In silicon/carbon complex system, material with carbon element is in charge and discharge process Middle Volume Changes be less than 10%, Stability Analysis of Structures, it as " skeleton " buffer silicon volumetric expansion, the structure of stable silicon, very big Cyclical stability is improved on degree.Silicon/carbon complex system can keep the feature of high power capacity, in Lithium-ion embeding and can take off again The stability of material structure is kept, therefore, silicon/carbon compound cathode materials are expected to become lithium ion battery of future generation and bear during going out Pole material.Generally in silicon/carbon composite, distribution in parent for the silicon mainly has cladded type, embedded type and molecule contacts type three Class.In the last few years, people also had a large amount of in-depth study to the selection of material with carbon element in silicon/carbon system, found a kind of suitable carbon Silicon grain is simultaneously combined the key being to study silicon/carbon composite by source in some way with material with carbon element.
Content of the invention
It is an object of the invention to provide a kind of lithium ion battery carbon/silicon/blocky graphite negative material, solve existing silicon and bear The problem of the lithium ion battery cyclical stability difference that pole material leads to because of huge Volume Changes during embedding de- lithium.
Second object of the present invention is to provide a kind of preparation of lithium ion battery carbon/silicon/blocky graphite negative material Method.
Third object of the present invention is to provide a kind of lithium-ion electric using above-mentioned carbon/silicon/blocky graphite negative material Pond.
In order to realize object above, the technical solution adopted in the present invention is：A kind of lithium ion battery carbon/silicon/bulk Graphite cathode material, including silicon/blocky graphite complex matrix, described silicon/blocky graphite complex matrix Surface coating has carbon-coating；Institute Stating silicon/blocky graphite complex matrix is the blocky graphite particle filling silica flour in surface hole defect.
In described silicon/blocky graphite complex matrix, the weight/mass percentage composition of silica flour is 0.1%～1.5%.
The D50 (median) of described carbon/silicon/blocky graphite negative material be 15～22 μm, tap density be 0.9～ 1.5g/cm3, specific surface area is 1.0～1.7m2/g.
A kind of preparation method of above-mentioned lithium ion battery carbon/silicon/blocky graphite negative material, comprises the following steps：
1) take blocky graphite particle and silica flour, silica flour is squeezed in the hole of blocky graphite particle surface, obtain silicon/bulk Graphite complex matrix；
2) by step 1) after gained silicon/blocky graphite complex matrix mixed with covering, heat up under protective atmosphere To 1000～1400 DEG C and be incubated 2～5h and carry out charing process, after being down to room temperature through screening, remove magnetic, obtain final product.
Step 1) in, the purity of described blocky graphite particle is that 99.95%～99.99%, D50 is 16.0～19.5 μm, Tap density is 0.9～1.1g/cm3, specific surface area is 5.0～7.0m2/ g, porosity is 9.5%～11.0%.
Step 1) in, the D50 of described silica flour is 0.1～0.5 μm.
Step 1) in, described extruding is blocky graphite particle and silica flour to be placed in RQM merge in balling machine, 800～ Work under the rotating speed of 1200rpm 0.5～1.5h, so that silica flour is squeezed in the hole of blocky graphite particle surface.
Step 2) in, described covering is pitch.
D50≤3 μm of described covering.
Step 2) in, silicon/blocky graphite complex matrix is 1 with the mass ratio of covering:0.03～0.06.
Step 2) in, described screening is to be sieved with the screen cloth of 200 mesh.
A kind of lithium ion battery, using above-mentioned silicon/carbon/blocky graphite negative material as negative material.
Blocky graphite, i.e. compact crystal shape graphite, belong to native graphite category, carbon content is 60%～65%, or even high Reach 80%～98%, crystallization naked eyes are visible, and crystal arrangement is disorderly and unsystematic, construct in compact massive；Blocky graphite is because of geologic origin It is different from natural flake graphite, this material internal space is big, has natural cellular pore space structure.
The lithium ion battery of present invention carbon/silicon/blocky graphite negative material, to fill the bulk of silica flour in surface hole defect Graphite granule is silicon/blocky graphite complex matrix, and silicon/blocky graphite complex matrix Surface coating has carbon-coating, blocky graphite surface There are a large amount of holes, these holes significantly increase the contact area of silica flour, cladding carbon-coating and matrix, increased the tight of binder course Density, the structure of gained carbon/silicon/graphite cathode material is more fine and close, improves the structural stability of negative material；Silica flour is filled Enter in the surface hole defect of blocky graphite particle, cladding carbon-coating makes cave fillings, is improve negative material capacity using silica flour On the basis of, on the one hand filling silica flour and cladding carbon-coating reduce the specific surface area of complex matrix, prevent from consuming excessive lithium ion Form SEI film, improve the reversible capacity of carbon-based material；Another aspect complex matrix coated with carbon bed prevents silicon grain exposed, The enormousness change that effectively buffering silicon grain produces in charge and discharge process, the volumetric expansion of suppression silicon, stabilize negative pole material Material structure, improves cyclical stability；Gained carbon/silicon/blocky graphite negative material has that tap density is high, reversible capacity is high, Capacity can design, the feature of stable cycle performance, little using the cathode pole piece bounce-back of this negative material preparation, expansion, thus carrying The high chemical property of lithium ion battery, improves its cyclical stability, extends its service life, meet market-oriented lithium ion The demand of battery high energy metric density, suitable popularization and application.
The preparation method of the lithium ion battery of present invention carbon/silicon/blocky graphite negative material, is that silica flour is squeezed into block Shape graphite granule obtains silicon/blocky graphite complex matrix, then through charing process more size-reduced after mixing with covering, sieve Divide, remove magnetic treatment, silica flour is sufficient filling with blocky graphite surface hole defect, covering forms carbon coated on complex matrix surface Layer, makes cave fillings, so that negative material, while improving capacity, prevents silicon grain exposed, effectively buffering silicon is embedding de- Enormousness change during lithium；So that gained carbon/silicon/blocky graphite negative material is had tap density is high, reversible capacity is high, Capacity can design, the feature of stable cycle performance；Can be by adjusting mass percent in silicon/blocky graphite complex matrix for the silicon Control the capacity of negative material；This preparation method process is simple, easy to operate, operation is few, low cost, and raw material sources extensively, are fitted Close large-scale industrial production.
Brief description
Fig. 1 is the carbon/silicon/bounce-back of cathode pole piece of blocky graphite negative material preparation of embodiment 1, expansion curve figure；
Fig. 2 is the discharge curve first of the lithium ion battery of carbon/silicon/blocky graphite negative material preparation of embodiment 1；
Fig. 3 is the cyclic curve of the full battery of lithium ion battery of carbon/silicon/blocky graphite negative material preparation of embodiment 1 Figure.
Specific embodiment
With reference to specific embodiment, the present invention is further illustrated.
Specific embodiment agents useful for same and raw material are commercial goods.
Embodiment 1
The lithium ion battery of the present embodiment carbon/silicon/blocky graphite negative material, including silicon/blocky graphite complex matrix, Described silicon/blocky graphite complex matrix Surface coating has carbon-coating；Described silicon/blocky graphite complex matrix is to fill in surface hole defect The blocky graphite particle of silica flour.
In described silicon/blocky graphite complex matrix, the weight/mass percentage composition of silica flour is 0.5%.Described carbon/silicon/bulk stone The D50 of black negative material is 18.43 μm, and tap density is 1.114g/cm3, specific surface area is 1.586m2/g.
The preparation method of the lithium ion battery of the present embodiment carbon/silicon/blocky graphite negative material, comprises the following steps：
1) purity is taken to be that 99.95%, D50 is 17.5 μm, tap density is 1.0g/cm3, specific surface area is 5.5m2/ g, hole Gap rate is 10.7% blocky graphite particle and D50 is 0.2 μm of silica flour, is placed in RQM and merges in balling machine, turning in 900rpm The lower 1h that works of speed, makes silica flour squeeze in the hole of blocky graphite particle surface, obtains silicon/blocky graphite complex matrix, wherein silicon The weight/mass percentage composition of powder is 0.5%；
2) by step 1) pitch of gained silicon/blocky graphite complex matrix and D50≤3 μm presses 1:0.05 mass ratio is mixed Mix in conjunction machine, be placed under nitrogen protection in airtight kiln, be warming up to 1000 DEG C and be incubated 5h and carry out charing process, fall Remove magnetic with 200 eye mesh screens screenings, degausser to room temperature, obtain final product D50 and be 18.43 μm, tap density is 1.114g/cm3, compare table Area is 1.586m2Carbon/silicon/blocky graphite the negative material of/g.
Conventionally gained carbon/silicon/blocky graphite negative material is made cathode pole piece, anti-to cathode pole piece Bullet, expansion character are detected, testing result is as shown in Figure 1.It will be seen from figure 1 that this cathode pole piece is anti-when in 4.2V Bullet, it is expanded to 26.09%；The cathode pole piece bounce-back respectively less than 27% of carbon/silicon/blocky graphite negative material preparation before full electricity, and When 100 to 400 week of following cycle, bounce-back is stablized in the range of 27～35%.
Carbon/silicon/blocky graphite the negative material of the present embodiment gained is made lithium ion battery negative, LiCoO2Make positive pole, 1MLiPF6+EC:EMC:DEC=1:1:1 system makees electrolyte, prepares the full battery of lithium ion battery, and tests its electrochemistry Can, testing result is as shown in Figure 2,3.
Fig. 2 is the discharge curve first of the lithium ion battery of carbon/silicon/blocky graphite negative material preparation, can from figure To find out, with carbon/silicon/lithium ion battery as negative pole for the blocky graphite negative material, discharge capacity is up to 1052.0mAh first.
Fig. 3 is carbon/silicon/lithium ion battery half-cell of blocky graphite negative material preparation, the cyclic curve figure of full battery. It can be seen that this lithium ion battery half-cell discharges first, gram volume is 389.2mAh/g, and coulombic efficiency reaches first 88.5%；The continuous circulation of full battery 100 weeks, 200 weeks, 300 weeks, 400 weeks when discharge capacity respectively 978.4mAh, 936.3mAh, 894.2mAh, 873.2mAh, the capability retention after discharge and recharge 400 weeks under 0.2C, 0.5C, 1C multiplying power is respectively For 85.98%, 84.87%, 82.56%；In whole 400 cyclic processes, capacitance loss rate is below 18%, fills through 400 times After discharge cycles, capability retention is maintained at 82.9%.
Embodiment 2
The lithium ion battery of the present embodiment carbon/silicon/blocky graphite negative material, including silicon/blocky graphite complex matrix, Described silicon/blocky graphite complex matrix Surface coating has carbon-coating；Described silicon/blocky graphite complex matrix is to fill in surface hole defect The blocky graphite particle of silica flour.
In described silicon/blocky graphite complex matrix, the weight/mass percentage composition of silica flour is 0.1%.Described carbon/silicon/bulk stone The D50 of black negative material is 19.34 μm, and tap density is 1.109g/cm3, specific surface area is 1.365m2/g.
The preparation method of the lithium ion battery of the present embodiment carbon/silicon/blocky graphite negative material, comprises the following steps：
1) purity is taken to be that 99.99%, D50 is 19.5 μm, tap density is 1.1g/cm3, specific surface area is 5.0m2/ g, hole Gap rate is 9.5% blocky graphite particle and D50 is 0.5 μm of silica flour, is placed in RQM and merges in balling machine, turning in 1000rpm The lower 0.5h that works of speed, makes silica flour squeeze in the hole of blocky graphite particle surface, obtains silicon/blocky graphite complex matrix, wherein The weight/mass percentage composition of silica flour is 0.1%；
2) by step 1) pitch of gained silicon/blocky graphite complex matrix and D50≤3 μm presses 1:0.06 mass ratio is mixed Mix in conjunction machine, be placed under nitrogen protection in airtight kiln, be warming up to 1400 DEG C and be incubated 2h and carry out charing process, fall Remove magnetic with 200 eye mesh screens screenings, degausser to room temperature, obtain final product D50 and be 19.34 μm, tap density is 1.109g/cm3, compare table Area is 1.365m2Carbon/silicon/blocky graphite the negative material of/g.
Using method same as Example 1, the present embodiment gained carbon/silicon/blocky graphite negative material is made negative pole Pole piece and lithium ion battery half-cell, full battery, and performance detection is carried out to it.Testing result shows, gained cathode pole piece exists Bounce-back during 4.2V, it is expanded to 25.76%.Described lithium ion battery half-cell discharges gram volume first for 380.4mAh/g；Entirely Coulombic efficiency reaches 86.8% to battery first, continuous circulation 100 weeks, 200 weeks, 300 weeks, 400 weeks when discharge capacity be respectively 975.2mAh, 922.2mAh, 890.4mAh, 837.4mAh, the capacity after discharge and recharge 400 weeks under 0.2C, 0.5C, 1C multiplying power is protected Holdup is respectively 83.89%, 82.97%, 80.32%.
Embodiment 3
The lithium ion battery of the present embodiment carbon/silicon/blocky graphite negative material, including silicon/blocky graphite complex matrix, Described silicon/blocky graphite complex matrix Surface coating has carbon-coating；Described silicon/blocky graphite complex matrix is to fill in surface hole defect The blocky graphite particle of silica flour.
In described silicon/blocky graphite complex matrix, the weight/mass percentage composition of silica flour is 0.5%.Described carbon/silicon/bulk stone The D50 of black negative material is 19.22 μm, and tap density is 1.102g/cm3, specific surface area is 1.446m2/g.
The preparation method of the lithium ion battery of the present embodiment carbon/silicon/blocky graphite negative material, comprises the following steps：
1) purity is taken to be that 99.98%, D50 is 19.5 μm, tap density is 1.1g/cm3, specific surface area is 5.0m2/ g, hole Gap rate is 9.5% blocky graphite particle and D50 is 0.5 μm of silica flour, is placed in RQM and merges in balling machine, turning in 1200rpm The lower 0.5h that works of speed, makes silica flour squeeze in the hole of blocky graphite particle surface, obtains silicon/blocky graphite complex matrix, wherein The weight/mass percentage composition of silica flour is 0.5%；
2) by step 1) pitch of gained silicon/blocky graphite complex matrix and D50≤3 μm presses 1:0.05 mass ratio is mixed Mix in conjunction machine, be placed under nitrogen protection in airtight kiln, be warming up to 1300 DEG C and be incubated 3h and carry out charing process, fall Remove magnetic with 200 eye mesh screens screenings, degausser to room temperature, obtain final product D50 and be 19.22 μm, tap density is 1.102g/cm3, compare table Area is 1.446m2Carbon/silicon/blocky graphite the negative material of/g.
Using method same as Example 1, the present embodiment gained carbon/silicon/blocky graphite negative material is made negative pole Pole piece and lithium ion battery half-cell, full battery, and performance detection is carried out to it.Testing result shows, gained cathode pole piece exists Bounce-back during 4.2V, it is expanded to 25.98%.Described lithium ion battery half-cell discharges gram volume first for 382.5mAh/g；Entirely Coulombic efficiency reaches 87.3% to battery first, continuous circulation 100 weeks, 200 weeks, 300 weeks, 400 weeks when discharge capacity be respectively 986.6mAh, 928.6mAh, 896.9mAh, 854.7mAh, the capacity after discharge and recharge 400 weeks under 0.2C, 0.5C, 1C multiplying power is protected Holdup is respectively 84.98%, 83.97%, 81.57%.
Embodiment 4
The lithium ion battery of the present embodiment carbon/silicon/blocky graphite negative material, including silicon/blocky graphite complex matrix, Described silicon/blocky graphite complex matrix Surface coating has carbon-coating；Described silicon/blocky graphite complex matrix is to fill in surface hole defect The blocky graphite particle of silica flour.
In described silicon/blocky graphite complex matrix, the weight/mass percentage composition of silica flour is 1.0%.Described carbon/silicon/bulk stone The D50 of black negative material is 19.05 μm, and tap density is 1.109g/cm3, specific surface area is 1.322m2/g.
The preparation method of the lithium ion battery of the present embodiment carbon/silicon/blocky graphite negative material, comprises the following steps：
1) purity is taken to be that 99.97%, D50 is 16.0 μm, tap density is 0.9g/cm3, specific surface area is 7.0m2/ g, hole Gap rate is 11.0% blocky graphite particle and D50 is 0.2 μm of silica flour, is placed in RQM and merges in balling machine, turning in 800rpm The lower 1.5h that works of speed, makes silica flour squeeze in the hole of blocky graphite particle surface, obtains silicon/blocky graphite complex matrix, wherein The weight/mass percentage composition of silica flour is 1.0%；
2) by step 1) pitch of gained silicon/blocky graphite complex matrix and D50≤3 μm presses 1:0.03 mass ratio is mixed Mix in conjunction machine, be placed under nitrogen protection in airtight kiln, be warming up to 1200 DEG C and be incubated 4h and carry out charing process, fall Remove magnetic with 200 eye mesh screens screenings, degausser to room temperature, obtain final product D50 and be 19.05 μm, tap density is 1.109g/cm3, compare table Area is 1.322m2Carbon/silicon/blocky graphite the negative material of/g.
Using method same as Example 1, the present embodiment gained carbon/silicon/blocky graphite negative material is made negative pole Pole piece and lithium ion battery half-cell, full battery, and performance detection is carried out to it.Testing result shows, gained cathode pole piece exists Bounce-back during 4.2V, it is expanded to 26.23%.Described lithium ion battery half-cell discharges gram volume first for 407.7mAh/g；Entirely Coulombic efficiency reaches 88.9% to battery first, continuous circulation 100 weeks, 200 weeks, 300 weeks, 400 weeks when discharge capacity be respectively 993.6mAh, 939.6mAh, 907.2mAh, 864.0mAh, the capacity after discharge and recharge 400 weeks under 0.2C, 0.5C, 1C multiplying power is protected Holdup is respectively 83.87%, 82.87%, 79.89%.
Embodiment 5
The lithium ion battery of the present embodiment carbon/silicon/blocky graphite negative material, including silicon/blocky graphite complex matrix, Described silicon/blocky graphite complex matrix Surface coating has carbon-coating；Described silicon/blocky graphite complex matrix is to fill in surface hole defect The blocky graphite particle of silica flour.
In described silicon/blocky graphite complex matrix, the weight/mass percentage composition of silica flour is 1.5%.Described carbon/silicon/bulk stone The D50 of black negative material is 19.24 μm, and tap density is 1.085g/cm3, specific surface area is 1.333m2/g.
The preparation method of the lithium ion battery of the present embodiment carbon/silicon/blocky graphite negative material, comprises the following steps：
1) purity is taken to be that 99.96%, D50 is 16.0 μm, tap density is 0.9g/cm3, specific surface area is 7.0m2/ g, hole Gap rate is 11.0% blocky graphite particle and D50 is 0.1 μm of silica flour, is placed in RQM and merges in balling machine, turning in 900rpm The lower 1h that works of speed, makes silica flour squeeze in the hole of blocky graphite particle surface, obtains silicon/blocky graphite complex matrix, wherein silicon The weight/mass percentage composition of powder is 1.5%；
2) by step 1) pitch of gained silicon/blocky graphite complex matrix and D50≤3 μm presses 1:0.04 mass ratio is mixed Mix in conjunction machine, be placed under nitrogen protection in airtight kiln, be warming up to 1100 DEG C and be incubated 5h and carry out charing process, fall Remove magnetic with 200 eye mesh screens screenings, degausser to room temperature, obtain final product D50 and be 19.24 μm, tap density is 1.085g/cm3, compare table Area is 1.333m2Carbon/silicon/blocky graphite the negative material of/g.
Using method same as Example 1, the present embodiment gained carbon/silicon/blocky graphite negative material is made negative pole Pole piece and lithium ion battery half-cell, full battery, and performance detection is carried out to it.Testing result shows, gained cathode pole piece exists Bounce-back during 4.2V, it is expanded to 26.37%.Described lithium ion battery half-cell discharges gram volume first for 420.4mAh/g, first Secondary coulombic efficiency reaches 88.1%；The continuous circulation of full battery 100 weeks, 200 weeks, 300 weeks, 400 weeks when discharge capacity be respectively 978.3mAh, 924.5mAh, 860.0mAh, 806.3mAh, the capacity after discharge and recharge 400 weeks under 0.2C, 0.5C, 1C multiplying power is protected Holdup is respectively 82.06%, 80.87%, 75.54%.
Experimental example
This experimental example is to embodiment 1～5 gained carbon/silicon/blocky graphite negative material and using the preparation of this negative material The full battery of cathode pole piece, lithium ion battery is detected.
Wherein, comparative example 1 is to change the blocky graphite in embodiment 1 into natural flake graphite, and remaining, with embodiment 1, obtains It is 17.69 μm to D50, tap density is 1.175g/cm3, specific surface area is 1.525m2Carbon/silicon/the natural flake graphite of/g is born Pole material, described carbon/silicon/natural flake graphite negative material is made cathode pole piece, lithium ion battery as described in Example 1 Half-cell, full battery simultaneously carry out performance detection.Testing result：The bounce-back in 4.2V for the gained cathode pole piece, it is expanded to 31.53%.Gained lithium ion battery half-cell discharges gram volume first for 371.9mAh/g, and coulombic efficiency reaches first 84.2%；The continuous circulation of full battery 100 weeks, 200 weeks, 300 weeks, 400 weeks when discharge capacity respectively 921.1mAh, 835.4mAh, 803.3mAh, 781.8mAh, the capability retention after discharge and recharge 400 weeks under 0.2C, 0.5C, 1C multiplying power is respectively For 83.89%, 77.98%, 73.67%.
The physical property testing result of embodiment 1～5 gained carbon/silicon/blocky graphite negative material is as shown in table 1.
The physical property testing result of table 1 embodiment 1～5 gained carbon/silicon/blocky graphite negative material
Sample D50 Tap density Specific surface area
(μm) (g/cm3) (m2/g)
Embodiment 1 18.43 1.114 1.586
Embodiment 2 19.34 1.109 1.365
Embodiment 3 19.22 1.102 1.446
Embodiment 4 19.05 1.109 1.322
Embodiment 5 19.24 1.085 1.333
Comparative example 1 17.69 1.175 1.525
The lithium ion battery half-cell that this experimental example assembles to embodiment 1～5 and the chemical property of full battery are examined Survey, testing result is as shown in table 2.
The lithium ion battery half-cell of table 2 embodiment 1～5 preparation, the electrochemical property test result of full battery
From table 2 it can be seen that the lithium-ion electric using embodiment 1～5 gained carbon/silicon/blocky graphite negative material preparation The electric discharge gram first that the gram volume of electric discharge first of pond half-cell is above the carbon/silicon/natural flake graphite obtained by comparative example 1 is held Amount, and full circulating battery to after 400 weeks its discharge capacity all in more than 800mAh, discharge capacity rate of decay is relatively low.Real Test result to show, the lithium ion battery using the carbon/silicon/blocky graphite negative material preparation of the present invention has excellent discharge and recharge Performance.
The high rate performance test result of the full battery of lithium ion battery of table 3 embodiment 1～5 preparation
From table 3 it can be seen that carbon/silicon/blocky graphite the material obtained by embodiment is dividing of the lithium ion battery of negative pole Capability retention after discharge and recharge 400 weeks not under 0.2C, 0.5C, 1C multiplying power is all higher than 75%, and higher than comparative example's Capability retention.Test result indicate that, using the lithium ion battery tool of the carbon/silicon/blocky graphite negative material preparation of the present invention There is excellent high rate performance.
The bounce-back of cathode pole piece of table 4 embodiment 1～5 preparation, expansion test result
Sample Embodiment 1 Embodiment 2 Embodiment 3 Embodiment 4 Embodiment 5 Comparative example 1
4.2V rebounds, (%) 26.09 25.76 25.98 26.23 26.37 31.53
From table 4, it can be seen that the bounce-back in 4.2V for the cathode pole piece obtained by embodiment 1～5, expanding and be respectively less than 27%, all little than comparative example.Test result indicate that, using the negative pole pole of the carbon/silicon/blocky graphite negative material preparation of the present invention Piece bounce-back, expansion are less.

Claims (9)

1. a kind of lithium ion battery carbon/silicon/blocky graphite negative material it is characterised in that：Including silicon/blocky graphite composite base Body, described silicon/blocky graphite complex matrix Surface coating has carbon-coating；Described silicon/blocky graphite complex matrix is in surface hole defect The blocky graphite particle of filling silica flour；In described silicon/blocky graphite complex matrix, the weight/mass percentage composition of silica flour is 0.1%～ 0.5%；Described lithium ion battery carbon/silicon/blocky graphite negative material is obtained by the method comprising the steps：
1) take blocky graphite particle and silica flour, silica flour is squeezed in the hole of blocky graphite particle surface, obtain silicon/bulk stone Black complex matrix；
2) by step 1) after gained silicon/blocky graphite complex matrix mixed with covering, it is warming up under protective atmosphere 1000～1400 DEG C and be incubated 2～5h and carry out charing process, after being down to room temperature through screening, remove magnetic, obtain final product.
2. the carbon of the lithium ion battery according to claim 1/silicon/blocky graphite negative material it is characterised in that：Described The D50 of carbon/silicon/blocky graphite negative material is 15～22 μm, and tap density is 0.9～1.5g/cm3, specific surface area be 1.0～ 1.7m2/g.
3. the preparation method of a kind of lithium ion battery as claimed in claim 1 carbon/silicon/blocky graphite negative material, it is special Levy and be：Comprise the following steps：
1) take blocky graphite particle and silica flour, silica flour is squeezed in the hole of blocky graphite particle surface, obtain silicon/bulk stone Black complex matrix；
2) by step 1) after gained silicon/blocky graphite complex matrix mixed with covering, it is warming up under protective atmosphere 1000～1400 DEG C and be incubated 2～5h and carry out charing process, after being down to room temperature through screening, remove magnetic, obtain final product.
4. the preparation method of lithium ion battery according to claim 3 carbon/silicon/blocky graphite negative material, it is special Levy and be：Step 1) in, the purity of described blocky graphite particle is that 99.95%～99.99%, D50 is 16.0～19.5 μm, Tap density is 0.9～1.1g/cm3, specific surface area is 5.0～7.0m2/ g, porosity is 9.5%～11.0%.
5. the preparation method of lithium ion battery according to claim 3 carbon/silicon/blocky graphite negative material, its feature It is：Step 1) in, the D50 of described silica flour is 0.1～0.5 μm.
6. the preparation method of lithium ion battery according to claim 3 carbon/silicon/blocky graphite negative material, its feature It is：Step 2) in, described covering is pitch.
7. the preparation method of the carbon of the lithium ion battery according to claim 3 or 6/silicon/blocky graphite negative material, it is special Levy and be：Step 2) in, silicon/blocky graphite complex matrix is 1 with the mass ratio of covering:0.03～0.06.
8. the preparation method of lithium ion battery according to claim 3 carbon/silicon/blocky graphite negative material, its feature It is：Step 2) in, described screening is to be sieved with the screen cloth of 200 mesh.
9. a kind of lithium ion battery it is characterised in that：Using the silicon/carbon described in claim 1/blocky graphite negative material conduct Negative material.
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Denomination of invention: Carbon / silicon / block graphite anode material for lithium ion battery, preparation method and lithium ion battery

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