CN104269521A - 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 PDFInfo
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- CN104269521A CN104269521A CN201410556823.2A CN201410556823A CN104269521A CN 104269521 A CN104269521 A CN 104269521A CN 201410556823 A CN201410556823 A CN 201410556823A CN 104269521 A CN104269521 A CN 104269521A
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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
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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
- 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
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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
- H01M4/139—Processes of manufacture
- H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
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- 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
Technical field
The invention belongs to technical field of lithium ion, be specifically related to a kind of lithium ion battery carbon/silicon/blocky graphite negative material, also relate to the preparation method of a kind of lithium ion battery carbon/silicon/blocky graphite negative material simultaneously and adopt the lithium ion battery of this negative material.
Background technology
Lithium ion battery becomes outshining othersOne branch of the tree is particularly thriving of energy storage field because having the advantages such as operating voltage is high, specific energy is high, electric discharge is steady, have extended cycle life, and has been widely used in the fields such as portable electric appts, electric tool, Aero-Space.Negative material enjoys people to pay close attention to as lithium ion battery critical material always.At present, although business-like graphite negative electrodes material excellent electrochemical performance, safe and reliable, its theoretical specific capacity is only 372mAh/g, can not meet the demand of people to high-energy-density, high rate capability lithium ion battery.For adapting to the demand in high power capacity, high-multiplying-power battery market, people start to try to explore and development of new negative material.
Silicon materials attract the eyeball of people with the ultra-high capacity of its 4200mAh/g, its rich reserves, environmentally friendly.But, silicon is as there is a fatal problem during lithium ion battery negative material, namely battery is attended by huge change in volume (> 300%) in charge and discharge process, after repeatedly repeated doff lithium, material there will be crackle, even powder of detached, causes cycle performance to fail, electrode failure.
At present, the method being commonly used to improve silicium cathode material circulation performance mainly contains silicon grain nanometer, silicon and inertia or active material compound etc., and wherein silicon/carbon composite is the most considerable.In silicon/carbon complex system, material with carbon element change in volume in charge and discharge process is less than 10%, Stability Analysis of Structures, and it cushions the volumetric expansion of silicon as " skeleton ", and the structure of stable silicon, improves cyclical stability to a great extent.Silicon/carbon complex system can keep the feature of high power capacity, again can in Lithium-ion embeding and the stability deviating from process to keep material structure, and therefore, silicon/carbon compound cathode materials is expected to become lithium ion battery negative material of future generation.In usual silicon/carbon composite, the distribution of silicon in parent mainly contains cladded type, embedded type and molecule contacts type three class.In the last few years, people also had research deep in a large number to the selection of material with carbon element in silicon/carbon system, and finding a kind of suitable carbon source and being carried out combining with material with carbon element in some way by silicon grain is the key studying silicon/carbon composite.
Summary of the invention
The object of this invention is to provide a kind of lithium ion battery carbon/silicon/blocky graphite negative material, solve the problem of the lithium ion battery cyclical stability difference that existing silicium cathode material causes because of huge change in volume in doff lithium process.
Second object of the present invention is to provide the preparation method of a kind of lithium ion battery carbon/silicon/blocky graphite negative material.
3rd object of the present invention is to provide a kind of lithium ion battery adopting above-mentioned carbon/silicon/blocky graphite negative material.
In order to realize above object, the technical solution adopted in the present invention is: a kind of lithium ion battery carbon/silicon/blocky graphite negative material, comprises silicon/blocky graphite complex matrix, and described silicon/blocky graphite complex matrix Surface coating has carbon-coating; Described silicon/blocky graphite complex matrix is the blocky graphite particle of filling silica flour in surface hole defect.
In described silicon/blocky graphite complex matrix, the mass percentage of silica flour is 0.1% ~ 1.5%.
The D50 (median) of described carbon/silicon/blocky graphite negative material is 15 ~ 22 μm, and tap density is 0.9 ~ 1.5g/cm
3, specific area is 1.0 ~ 1.7m
2/ g.
A preparation method for above-mentioned lithium ion battery carbon/silicon/blocky graphite negative material, comprises the following steps:
1) get blocky graphite particle and silica flour, silica flour is squeezed in the hole of blocky graphite particle surface, obtain silicon/blocky graphite complex matrix;
2) by step 1) after gained silicon/blocky graphite complex matrix mixes with covering, under protective atmosphere, be warming up to 1000 ~ 1400 DEG C and be incubated 2 ~ 5h and carry out charing process, through screening, except magnetic, to obtain final product after being down to room temperature.
Step 1) in, the purity of described blocky graphite particle is 99.95% ~ 99.99%, D50 is 16.0 ~ 19.5 μm, and tap density is 0.9 ~ 1.1g/cm
3, specific area is 5.0 ~ 7.0m
2/ 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 blocky graphite particle and silica flour is placed in RQM to merge balling machine, and work 0.5 ~ 1.5h under the rotating speed of 800 ~ 1200rpm, and 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, the mass ratio of silicon/blocky graphite complex matrix and covering is 1:0.03 ~ 0.06.
Step 2) in, described screening is sieved with 200 object screen clothes.
A kind of lithium ion battery, adopts above-mentioned silicon/carbon/blocky graphite negative material as negative material.
Blocky graphite, i.e. compact crystal shape graphite, belong to native graphite category, and carbon content is 60% ~ 65%, and even up to 80% ~ 98%, crystallization naked eyes are visible, and crystal arrangement is disorderly and unsystematic, construct in compact massive; Blocky graphite is different from natural flake graphite because of geologic origin, and this material internal space is large, has natural cellular pore space structure.
Lithium ion battery carbon/silicon/blocky graphite negative material of the present invention, to fill the blocky graphite particle of silica flour in surface hole defect for silicon/blocky graphite complex matrix, silicon/blocky graphite complex matrix Surface coating has carbon-coating, there is a large amount of hole in blocky graphite surface, these holes increase the contact area of silica flour, coated carbon-coating and matrix greatly, add the tightness of binder course, 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 in the surface hole defect of blocky graphite particle, coated carbon-coating makes cave fillings, improve on the basis of negative material capacity utilizing silica flour, filling silica flour and coated carbon-coating reduce the specific area of complex matrix on the one hand, prevent consuming too much lithium ion and form SEI film, improve the reversible capacity of carbon-based material; Complex matrix coated with carbon bed prevents silicon grain exposed on the other hand, and the enormousness that effectively buffering silicon grain produces in charge and discharge process changes, and suppresses the volumetric expansion of silicon, stabilizes negative material structure, improve 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, the cathode pole piece adopting this negative material to prepare rebounds, it is little to expand, thus improve the chemical property of lithium ion battery, improve its cyclical stability, extend its useful life, meet the demand of market-oriented lithium ion battery high-energy-density, be applicable to applying.
The preparation method of lithium ion battery carbon/silicon/blocky graphite negative material of the present invention, silica flour is squeezed into blocky graphite particle to obtain silicon/blocky graphite complex matrix, through charing process after mixing with covering again, again through pulverizing, sieving, except magnetic treatment, silica flour is fully filled in blocky graphite surface hole defect, covering forms coated carbon-coating on complex matrix surface, make cave fillings, thus make negative material while raising capacity, prevent silicon grain exposed, the effectively enormousness change of buffering silicon in doff lithium process; Gained carbon/silicon/blocky graphite negative material is had, and tap density is high, reversible capacity is high, capacity can design, the feature of stable cycle performance; The capacity of negative material is controlled by the mass percent of adjustment silicon in silicon/blocky graphite complex matrix; This preparation method's technique is simple, and easy to operate, operation is few, and cost is low, and raw material sources are extensive, is applicable to large-scale industrial production.
Accompanying drawing explanation
Fig. 1 is bounce-back, the expansion curve figure of cathode pole piece prepared by the carbon/silicon/blocky graphite negative material of embodiment 1;
Fig. 2 is the discharge curve first of lithium ion battery prepared by the carbon/silicon/blocky graphite negative material of embodiment 1;
Fig. 3 is the cyclic curve figure of the full battery of lithium ion battery prepared by the carbon/silicon/blocky graphite negative material of embodiment 1.
Embodiment
Below in conjunction with embodiment, the present invention is further illustrated.
Embodiment agents useful for same and raw material are commercial goods.
Embodiment 1
Lithium ion battery carbon/silicon/blocky graphite the negative material of the present embodiment, comprises silicon/blocky graphite complex matrix, and described silicon/blocky graphite complex matrix Surface coating has carbon-coating; Described silicon/blocky graphite complex matrix is the blocky graphite particle of filling silica flour in surface hole defect.
In described silicon/blocky graphite complex matrix, the mass percentage of silica flour is 0.5%.The D50 of described carbon/silicon/blocky graphite negative material is 18.43 μm, and tap density is 1.114g/cm
3, specific area is 1.586m
2/ g.
The preparation method of the lithium ion battery carbon/silicon/blocky graphite negative material of the present embodiment, comprises the following steps:
1) to get purity be 99.95%, D50 is 17.5 μm, and tap density is 1.0g/cm
3, specific area is 5.5m
2/ g, porosity be 10.7% blocky graphite particle and D50 be the silica flour of 0.2 μm, be placed in RQM and merge balling machine, work 1h under the rotating speed of 900rpm, silica flour is made to squeeze in the hole of blocky graphite particle surface, obtain silicon/blocky graphite complex matrix, wherein the mass percentage of silica flour is 0.5%;
2) by step 1) pitch of gained silicon/blocky graphite complex matrix and D50≤3 μm mixes in mixer by the mass ratio of 1:0.05; be placed in airtight kiln under nitrogen protection; be warming up to 1000 DEG C and be incubated 5h and carry out charing process; magnetic is removed with 200 eye mesh screen screenings, degausser after being down to room temperature; obtaining D50 is 18.43 μm, and tap density is 1.114g/cm
3, specific area is 1.586m
2carbon/silicon/blocky graphite the negative material of/g.
Conventionally gained carbon/silicon/blocky graphite negative material is made cathode pole piece, bounce-back, the expansion character of anticathode pole piece detect, and testing result as shown in Figure 1.As can be seen from Figure 1, the bounce-back of this cathode pole piece when at 4.2V, 26.09% is expanded to; The cathode pole piece bounce-back that before full electricity prepared by carbon/silicon/blocky graphite negative material is all less than 27%, and when following cycle 100 to 400 week, bounce-back is stabilized in 27 ~ 35% scopes.
Carbon/silicon/blocky graphite the negative material of the present embodiment gained is made lithium ion battery negative, LiCoO
2make positive pole, 1MLiPF
6+ EC:EMC:DEC=1:1:1 system makes electrolyte, and prepare the full battery of lithium ion battery, and test its chemical property, testing result as shown in Figure 2,3.
Fig. 2 is the discharge curve first of lithium ion battery prepared by carbon/silicon/blocky graphite negative material, as can be seen from the figure, the lithium ion battery being negative pole with carbon/silicon/blocky graphite negative material first discharge capacity up to 1052.0mAh.
Fig. 3 is the cyclic curve figure of lithium ion battery half-cell, full battery prepared by carbon/silicon/blocky graphite negative material.As can be seen from the figure, this lithium ion battery half-cell gram volume that discharges first is 389.2mAh/g, and coulombic efficiency reaches 88.5% first; During full battery continuous circulation 100 weeks, 200 weeks, 300 weeks, 400 weeks, discharge capacity is respectively 978.4mAh, 936.3mAh, 894.2mAh, 873.2mAh, and under 0.2C, 0.5C, 1C multiplying power, the capability retention of discharge and recharge after 400 weeks is respectively 85.98%, 84.87%, 82.56%; In whole 400 cyclic processes, capacitance loss rate is all lower than 18%, and after 400 charge and discharge cycles, capability retention remains on 82.9%.
Embodiment 2
Lithium ion battery carbon/silicon/blocky graphite the negative material of the present embodiment, comprises silicon/blocky graphite complex matrix, and described silicon/blocky graphite complex matrix Surface coating has carbon-coating; Described silicon/blocky graphite complex matrix is the blocky graphite particle of filling silica flour in surface hole defect.
In described silicon/blocky graphite complex matrix, the mass percentage of silica flour is 0.1%.The D50 of described carbon/silicon/blocky graphite negative material is 19.34 μm, and tap density is 1.109g/cm
3, specific area is 1.365m
2/ g.
The preparation method of the lithium ion battery carbon/silicon/blocky graphite negative material of the present embodiment, comprises the following steps:
1) to get purity be 99.99%, D50 is 19.5 μm, and tap density is 1.1g/cm
3, specific area is 5.0m
2/ g, porosity be 9.5% blocky graphite particle and D50 be the silica flour of 0.5 μm, be placed in RQM and merge balling machine, work 0.5h under the rotating speed of 1000rpm, silica flour is made to squeeze in the hole of blocky graphite particle surface, obtain silicon/blocky graphite complex matrix, wherein the mass percentage of silica flour is 0.1%;
2) by step 1) pitch of gained silicon/blocky graphite complex matrix and D50≤3 μm mixes in mixer by the mass ratio of 1:0.06; be placed in airtight kiln under nitrogen protection; be warming up to 1400 DEG C and be incubated 2h and carry out charing process; magnetic is removed with 200 eye mesh screen screenings, degausser after being down to room temperature; obtaining D50 is 19.34 μm, and tap density is 1.109g/cm
3, specific area is 1.365m
2carbon/silicon/blocky graphite the negative material of/g.
Adopt the method identical with embodiment 1, the present embodiment gained carbon/silicon/blocky graphite negative material is made cathode pole piece and lithium ion battery half-cell, full battery, and Performance Detection is carried out to it.Testing result shows, the bounce-back of gained cathode pole piece when 4.2V, is expanded to 25.76%.The described lithium ion battery half-cell gram volume that discharges first is 380.4mAh/g; Full battery first coulombic efficiency reaches 86.8%, during continuous circulation 100 weeks, 200 weeks, 300 weeks, 400 weeks, discharge capacity is respectively 975.2mAh, 922.2mAh, 890.4mAh, 837.4mAh, and under 0.2C, 0.5C, 1C multiplying power, the capability retention of discharge and recharge after 400 weeks is respectively 83.89%, 82.97%, 80.32%.
Embodiment 3
Lithium ion battery carbon/silicon/blocky graphite the negative material of the present embodiment, comprises silicon/blocky graphite complex matrix, and described silicon/blocky graphite complex matrix Surface coating has carbon-coating; Described silicon/blocky graphite complex matrix is the blocky graphite particle of filling silica flour in surface hole defect.
In described silicon/blocky graphite complex matrix, the mass percentage of silica flour is 0.5%.The D50 of described carbon/silicon/blocky graphite negative material is 19.22 μm, and tap density is 1.102g/cm
3, specific area is 1.446m
2/ g.
The preparation method of the lithium ion battery carbon/silicon/blocky graphite negative material of the present embodiment, comprises the following steps:
1) to get purity be 99.98%, D50 is 19.5 μm, and tap density is 1.1g/cm
3, specific area is 5.0m
2/ g, porosity be 9.5% blocky graphite particle and D50 be the silica flour of 0.5 μm, be placed in RQM and merge balling machine, work 0.5h under the rotating speed of 1200rpm, silica flour is made to squeeze in the hole of blocky graphite particle surface, obtain silicon/blocky graphite complex matrix, wherein the mass percentage of silica flour is 0.5%;
2) by step 1) pitch of gained silicon/blocky graphite complex matrix and D50≤3 μm mixes in mixer by the mass ratio of 1:0.05; be placed in airtight kiln under nitrogen protection; be warming up to 1300 DEG C and be incubated 3h and carry out charing process; magnetic is removed with 200 eye mesh screen screenings, degausser after being down to room temperature; obtaining D50 is 19.22 μm, and tap density is 1.102g/cm
3, specific area is 1.446m
2carbon/silicon/blocky graphite the negative material of/g.
Adopt the method identical with embodiment 1, the present embodiment gained carbon/silicon/blocky graphite negative material is made cathode pole piece and lithium ion battery half-cell, full battery, and Performance Detection is carried out to it.Testing result shows, the bounce-back of gained cathode pole piece when 4.2V, is expanded to 25.98%.The described lithium ion battery half-cell gram volume that discharges first is 382.5mAh/g; Full battery first coulombic efficiency reaches 87.3%, during continuous circulation 100 weeks, 200 weeks, 300 weeks, 400 weeks, discharge capacity is respectively 986.6mAh, 928.6mAh, 896.9mAh, 854.7mAh, and under 0.2C, 0.5C, 1C multiplying power, the capability retention of discharge and recharge after 400 weeks is respectively 84.98%, 83.97%, 81.57%.
Embodiment 4
Lithium ion battery carbon/silicon/blocky graphite the negative material of the present embodiment, comprises silicon/blocky graphite complex matrix, and described silicon/blocky graphite complex matrix Surface coating has carbon-coating; Described silicon/blocky graphite complex matrix is the blocky graphite particle of filling silica flour in surface hole defect.
In described silicon/blocky graphite complex matrix, the mass percentage of silica flour is 1.0%.The D50 of described carbon/silicon/blocky graphite negative material is 19.05 μm, and tap density is 1.109g/cm
3, specific area is 1.322m
2/ g.
The preparation method of the lithium ion battery carbon/silicon/blocky graphite negative material of the present embodiment, comprises the following steps:
1) to get purity be 99.97%, D50 is 16.0 μm, and tap density is 0.9g/cm
3, specific area is 7.0m
2/ g, porosity be 11.0% blocky graphite particle and D50 be the silica flour of 0.2 μm, be placed in RQM and merge balling machine, work 1.5h under the rotating speed of 800rpm, silica flour is made to squeeze in the hole of blocky graphite particle surface, obtain silicon/blocky graphite complex matrix, wherein the mass percentage of silica flour is 1.0%;
2) by step 1) pitch of gained silicon/blocky graphite complex matrix and D50≤3 μm mixes in mixer by the mass ratio of 1:0.03; be placed in airtight kiln under nitrogen protection; be warming up to 1200 DEG C and be incubated 4h and carry out charing process; magnetic is removed with 200 eye mesh screen screenings, degausser after being down to room temperature; obtaining D50 is 19.05 μm, and tap density is 1.109g/cm
3, specific area is 1.322m
2carbon/silicon/blocky graphite the negative material of/g.
Adopt the method identical with embodiment 1, the present embodiment gained carbon/silicon/blocky graphite negative material is made cathode pole piece and lithium ion battery half-cell, full battery, and Performance Detection is carried out to it.Testing result shows, the bounce-back of gained cathode pole piece when 4.2V, is expanded to 26.23%.The described lithium ion battery half-cell gram volume that discharges first is 407.7mAh/g; Full battery first coulombic efficiency reaches 88.9%, during continuous circulation 100 weeks, 200 weeks, 300 weeks, 400 weeks, discharge capacity is respectively 993.6mAh, 939.6mAh, 907.2mAh, 864.0mAh, and under 0.2C, 0.5C, 1C multiplying power, the capability retention of discharge and recharge after 400 weeks is respectively 83.87%, 82.87%, 79.89%.
Embodiment 5
Lithium ion battery carbon/silicon/blocky graphite the negative material of the present embodiment, comprises silicon/blocky graphite complex matrix, and described silicon/blocky graphite complex matrix Surface coating has carbon-coating; Described silicon/blocky graphite complex matrix is the blocky graphite particle of filling silica flour in surface hole defect.
In described silicon/blocky graphite complex matrix, the mass percentage of silica flour is 1.5%.The D50 of described carbon/silicon/blocky graphite negative material is 19.24 μm, and tap density is 1.085g/cm
3, specific area is 1.333m
2/ g.
The preparation method of the lithium ion battery carbon/silicon/blocky graphite negative material of the present embodiment, comprises the following steps:
1) to get purity be 99.96%, D50 is 16.0 μm, and tap density is 0.9g/cm
3, specific area is 7.0m
2/ g, porosity be 11.0% blocky graphite particle and D50 be the silica flour of 0.1 μm, be placed in RQM and merge balling machine, work 1h under the rotating speed of 900rpm, silica flour is made to squeeze in the hole of blocky graphite particle surface, obtain silicon/blocky graphite complex matrix, wherein the mass percentage of silica flour is 1.5%;
2) by step 1) pitch of gained silicon/blocky graphite complex matrix and D50≤3 μm mixes in mixer by the mass ratio of 1:0.04; be placed in airtight kiln under nitrogen protection; be warming up to 1100 DEG C and be incubated 5h and carry out charing process; magnetic is removed with 200 eye mesh screen screenings, degausser after being down to room temperature; obtaining D50 is 19.24 μm, and tap density is 1.085g/cm
3, specific area is 1.333m
2carbon/silicon/blocky graphite the negative material of/g.
Adopt the method identical with embodiment 1, the present embodiment gained carbon/silicon/blocky graphite negative material is made cathode pole piece and lithium ion battery half-cell, full battery, and Performance Detection is carried out to it.Testing result shows, the bounce-back of gained cathode pole piece when 4.2V, is expanded to 26.37%.The described lithium ion battery half-cell gram volume that discharges first is 420.4mAh/g, and coulombic efficiency reaches 88.1% first; During full battery continuous circulation 100 weeks, 200 weeks, 300 weeks, 400 weeks, discharge capacity is respectively 978.3mAh, 924.5mAh, 860.0mAh, 806.3mAh, and under 0.2C, 0.5C, 1C multiplying power, the capability retention of discharge and recharge after 400 weeks is respectively 82.06%, 80.87%, 75.54%.
Experimental example
This experimental example detects embodiment 1 ~ 5 gained carbon/silicon/blocky graphite negative material and the cathode pole piece adopting this negative material to prepare, the full battery of lithium ion battery.
Wherein, comparative example 1 changes the blocky graphite in embodiment 1 into natural flake graphite, and all the other are with embodiment 1, and obtaining D50 is 17.69 μm, and tap density is 1.175g/cm
3, specific area is 1.525m
2carbon/silicon/natural flake graphite the negative material of/g, makes cathode pole piece, lithium ion battery half-cell, full battery carry out Performance Detection by described carbon/silicon/natural flake graphite negative material by the method for embodiment 1.Testing result: the bounce-back of gained cathode pole piece when 4.2V, be expanded to 31.53%.The gained lithium ion battery half-cell gram volume that discharges first is 371.9mAh/g, and coulombic efficiency reaches 84.2% first; During full battery continuous circulation 100 weeks, 200 weeks, 300 weeks, 400 weeks, discharge capacity is respectively 921.1mAh, 835.4mAh, 803.3mAh, 781.8mAh, and under 0.2C, 0.5C, 1C multiplying power, the capability retention of discharge and recharge after 400 weeks is respectively 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 area |
| (μm) | (g/cm 3) | (m 2/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 chemical property of the lithium ion battery half-cell that this experimental example is assembled embodiment 1 ~ 5 and full battery detects, and testing result is as shown in table 2.
Lithium ion battery half-cell prepared by table 2 embodiment 1 ~ 5, the electrochemical property test result of full battery
As can be seen from Table 2, the gram volume that discharges first of the lithium ion battery half-cell adopting embodiment 1 ~ 5 gained carbon/silicon/blocky graphite negative material to prepare is all higher than the gram volume of electric discharge first of the carbon/silicon/natural flake graphite obtained by comparative example 1, and its discharge capacity is all at more than 800mAh after full circulating battery to 400 week, discharge capacity rate of decay is relatively low.Experimental result shows, adopts the lithium ion battery that carbon/silicon/prepared by blocky graphite negative material of the present invention to have excellent charge-discharge performance.
The high rate performance test result of the full battery of lithium ion battery prepared by table 3 embodiment 1 ~ 5
As can be seen from Table 3, the carbon/silicon/blocky graphite material obtained by embodiment be the lithium ion battery of negative pole respectively under 0.2C, 0.5C, 1C multiplying power the capability retention of discharge and recharge after 400 weeks be all greater than 75%, and higher than the capability retention of comparative example.Experimental result shows, adopts the lithium ion battery that carbon/silicon/prepared by blocky graphite negative material of the present invention to have excellent high rate performance.
The bounce-back of cathode pole piece prepared by table 4 embodiment 1 ~ 5, 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 |
As can be seen from Table 4, the bounce-back of the cathode pole piece obtained by embodiment 1 ~ 5 when 4.2V, expansion are all less than 27%, all little than comparative example.Experimental result shows, the cathode pole piece adopting carbon/silicon/blocky graphite negative material of the present invention to prepare rebounds, it is less to expand.
Claims (10)
1. lithium ion battery carbon/silicon/blocky graphite negative material, is characterized in that: comprise silicon/blocky graphite complex matrix, described silicon/blocky graphite complex matrix Surface coating has carbon-coating; Described silicon/blocky graphite complex matrix is the blocky graphite particle of filling silica flour in surface hole defect.
2. lithium ion battery carbon/silicon/blocky graphite negative material according to claim 1, is characterized in that: in described silicon/blocky graphite complex matrix, and the mass percentage of silica flour is 0.1% ~ 1.5%.
3. lithium ion battery carbon/silicon/blocky graphite negative material according to claim 1 and 2, is characterized in that: the D50 of described carbon/silicon/blocky graphite negative material is 15 ~ 22 μm, and tap density is 0.9 ~ 1.5g/cm
3, specific area is 1.0 ~ 1.7m
2/ g.
4. a preparation method for lithium ion battery carbon/silicon/blocky graphite negative material as claimed in claim 1, is characterized in that: comprise the following steps:
1) get blocky graphite particle and silica flour, silica flour is squeezed in the hole of blocky graphite particle surface, obtain silicon/blocky graphite complex matrix;
2) by step 1) after gained silicon/blocky graphite complex matrix mixes with covering, under protective atmosphere, be warming up to 1000 ~ 1400 DEG C and be incubated 2 ~ 5h and carry out charing process, through screening, except magnetic, to obtain final product after being down to room temperature.
5. the preparation method of lithium ion battery carbon/silicon/blocky graphite negative material according to claim 4, it is characterized in that: step 1) in, the purity of described blocky graphite particle is 99.95% ~ 99.99%, D50 is 16.0 ~ 19.5 μm, and tap density is 0.9 ~ 1.1g/cm
3, specific area is 5.0 ~ 7.0m
2/ g, porosity is 9.5% ~ 11.0%.
6. the preparation method of lithium ion battery carbon/silicon/blocky graphite negative material according to claim 4, is characterized in that: step 1) in, the D50 of described silica flour is 0.1 ~ 0.5 μm.
7. the preparation method of lithium ion battery carbon/silicon/blocky graphite negative material according to claim 4, is characterized in that: step 2) in, described covering is pitch.
8. the preparation method of the carbon of the lithium ion battery according to claim 4 or 7/silicon/blocky graphite negative material, is characterized in that: step 2) in, the mass ratio of silicon/blocky graphite complex matrix and covering is 1:0.03 ~ 0.06.
9. the preparation method of lithium ion battery carbon/silicon/blocky graphite negative material according to claim 4, is characterized in that: step 2) in, described screening is sieved with 200 object screen clothes.
10. a lithium ion battery, is characterized in that: adopt silicon/carbon/blocky graphite negative material according to claim 1 as negative material.
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