CN104393298B - A kind of lithium ion battery blocky graphite negative material, preparation method and lithium ion battery - Google Patents
A kind of lithium ion battery blocky graphite negative material, preparation method and lithium ion battery Download PDFInfo
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- CN104393298B CN104393298B CN201410556821.3A CN201410556821A CN104393298B CN 104393298 B CN104393298 B CN 104393298B CN 201410556821 A CN201410556821 A CN 201410556821A CN 104393298 B CN104393298 B CN 104393298B
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Abstract
The invention discloses a kind of lithium ion battery blocky graphite negative material, preparation method and lithium ion battery, this negative material includes blocky graphite matrix, and described blocky graphite matrix surface is coated with graphite coat layer.The lithium ion battery of present invention blocky graphite negative material, there is a large amount of micropore in blocky graphite matrix surface, coated rear graphite coat layer is good with the associativity of blocky graphite matrix, inter-molecular binding force is strong, tap density is high, reversible specific capacity is high, the advantage of good rate capability to make blocky graphite negative material have, using negative plate bounce-back prepared by this blocky graphite negative material, expanding little, the lithium ion battery of preparation has good chemical property；This blocky graphite negative material has expanded the purposes of blocky graphite, improves native graphite added value of product, expands the development space in lithium ion battery negative material source；This negative material can be used as the negative material of the lithium ion batteries such as aluminum hull, Soft Roll and cylinder, has broad application prospects.
Description
Technical field
The invention belongs to technical field of lithium ion, be specifically related to a kind of lithium ion battery blocky graphite negative pole material
Material, also relates to the preparation method of a kind of lithium ion battery blocky graphite negative material and uses this blocky graphite negative pole material
The lithium ion battery of material.
Background technology
Compared with traditional plumbic acid, NI-G secondary cell, lithium ion battery has operating voltage height, specific energy height, work
Temperature range width, electric discharge steadily, have extended cycle life, the advantage such as memory-less effect, therefore it is wide as a kind of novel energy-storing power supply
It general is applied to the fields such as communication equipment, electric tool, Aero-Space.At present, with the continuous progress of technology, people are to lithium ion
Battery is had higher requirement, and has the performances such as high-energy-density, high rate capability, long circulation life, high safety factor
Lithium ion battery is increasingly becoming the study hotspot of people.
As one of lithium ion battery critical material, negative material enjoys the concern of people always.Lithium ion battery negative
Material need to meet following characteristics: 1) oxidation-reduction potential is close to lithium current potential；2) lithium ion inserts and abjection should be reversible；3) lithium ion
In material of main part, diffusion coefficient is big；4) in charge and discharge process, agent structure is stable；5) electronics and ionic conductivity are high；6) price
Cheaply, pollution-free.In current material, graphite is because of features such as it is with low cost, good processability, good conductivity, stable performances
And become the main flow of lithium ion battery negative material.
Native graphite is very abundant at China's reserves, cheap, and degree of crystallinity is high, is that production at present is upper widely used
One of negative material.Different according to crystal habit, native graphite can be divided into compact crystal shape graphite, crystalline flake graphite, cryptocrystalline stone
Ink three classes, wherein compact crystal shape graphite is also referred to as blocky graphite, and this graphite is formed by pneumatolysis.Blocky graphite product
Position is very high, and carbon content is 60%～65%, and even as high as 80%～98%, crystallization naked eyes are visible, and crystal arrangement is disorderly and unsystematic, in
Compact massive constructs.At present, researcher has mainly carried out numerous studies to crystalline flake graphite as lithium ion battery negative material,
Blocky graphite then rarely has research.Therefore, for expanding the purposes of blocky graphite, sending out of lithium ion battery negative material source is expanded
Exhibition space, develops one of a kind of blocky graphite negative material important research direction becoming lithium ion battery.
Content of the invention
It is an object of the invention to provide a kind of lithium ion battery blocky graphite negative material.
Second object of the present invention is to provide the preparation method of a kind of lithium ion battery blocky graphite negative material.
Third object of the present invention is to provide a kind of lithium ion battery using above-mentioned blocky graphite negative material.
In order to realize object above, the technical solution adopted in the present invention is: a kind of lithium ion battery blocky graphite is born
Pole material, including blocky graphite matrix, described blocky graphite matrix surface is coated with graphite coat layer.
The D50 (median) of this blocky graphite negative material is 12～20 μm, and tap density is 0.8～1.3g/cm3,
Specific surface area is 1.1～2.4m2/g。
A kind of above-mentioned lithium ion battery preparation method of blocky graphite negative material, comprises the following steps:
1) take after blocky graphite matrix mixes with covering, under protective atmosphere, be warming up to 1000～1400 DEG C and protect
Temperature 2～5h carry out charing process, after be down to room temperature, obtain carbonized material；
2) by step 1) gained carbonized material is incubated 5～7h under the conditions of 2500～3000 DEG C and carries out graphitization processing, be down to
After room temperature more screened, remove magnetic treatment, to obtain final product.
Step 1) described in the mass ratio of blocky graphite matrix and covering be 1:0.03～0.06.
Described covering is pitch, furane resins or ethylene-ethylacrylate resin (EAA resin).
D50≤3 μm of described covering.
Step 1) in, the purity of described blocky graphite matrix is 99.95%～99.99%, and D50 is 8.5～17.5 μm, shakes
Real density is 0.8～1.0g/cm3, specific surface area is 5.5～9.5m2/g。
Described blocky graphite matrix is prepared by following methods:
Take blocky graphite particle, pulverize, use after alkali acid system carries out chemical purification, cleaned, be dried after, high temperature purification,
After being down to room temperature, secondary smashes and i.e. obtains blocky graphite matrix again.
Described blocky graphite matrix can be mixed by the different blocky graphite particle of D50.
The 80%～95% of described blocky graphite particle, D50 is 25～100 μm.
Described pulverizing refers to pulverize and be classified select the particle that D50 is 20～30 μm.
Described alkali acid system is by the quality of 1:0.2～0.4:0.6～0.8 by blocky graphite, NaOH solid and deionized water
Melt 1～2h than alkali at 500～600 DEG C, washing and after being dried again with the hydrochloric acid that concentration is 13%～17% at 70～90 DEG C of bars
Constant temperature acidleach 2～3h under part, finally washing is simultaneously dried.
Described cleaning is to clean 1～4 time by deionized water.
Described drying is to be dried 3～10h under the conditions of 50～120 DEG C.
Described high temperature purification is insulation 0.5～1.5h under the conditions of 2000～3000 DEG C.
Described secondary smashes and refers to pulverize and be classified select the particle that D50 is 8.5～17.5 μm.
Step 2) in, described screening is with 200～250 eye mesh screen screenings.
A kind of lithium ion battery, uses above-mentioned blocky graphite negative material as negative material.
The lithium ion battery of present invention blocky graphite negative material, is that blocky graphite matrix surface is coated with graphite coat
Layer, there is a large amount of micropore in blocky graphite matrix surface, these micropores significantly increase the contact area of covering and matrix, increases
The tight ness rating of binder course so that the structure of end product blocky graphite is more fine and close；Coated rear graphite coat layer and bulk
The associativity of graphite matrix is good, and inter-molecular binding force is strong, tap density is high, reversible specific capacity to make blocky graphite negative material have
High, the advantage of good rate capability, use negative plate bounce-back prepared by this blocky graphite negative material, expand little, the lithium of preparation from
Sub-battery has good chemical property, meets people and follows for lithium ion battery high-energy-density, high rate capability, length
Ring life-span, the requirement of high safety factor；This blocky graphite negative material has expanded the purposes of blocky graphite, improves native graphite
Added value of product, expands the development space in lithium ion battery negative material source；This negative material can be used as aluminum hull, Soft Roll and
The negative material of the lithium ion batteries such as cylinder, has broad application prospects.
The lithium ion battery of the present invention preparation method of blocky graphite negative material, is by blocky graphite matrix and cladding
After agent mixes, pulverizing after charing, graphitization processing again, sieve, removing magnetic, gained blocky graphite negative material has well
Chemical property, reversible specific capacity, efficiency for charge-discharge, stable cycle performance and the high rate performance of lithium ion battery can be improved；
This preparation method technique is simple, easy to operate, and raw material sources are extensive, low cost, is suitable for large-scale industrial production.
Further, blocky graphite matrix is through smashing, chemical purification, washing, drying, sieve by blocky graphite raw material
Point, then after high temperature secondary purification, the purity obtaining is the blocky graphite particle of 99.95%～99.99%, high temperature purification one side
Face makes graphite purity be improved, and on the other hand makes the further graphitization of graphite, thus improves the graphite of blocky graphite
Change degree, thus improve the quality of blocky graphite matrix.
Brief description
Fig. 1 is the bounce-back of the negative plate that embodiment 1 gained blocky graphite negative material is made, expansion curve figure.
The electric discharge first of the full battery of lithium ion battery that Fig. 2 assembles for using embodiment 1 gained blocky graphite negative material
Curve map；
The cyclic curve of the full battery of lithium ion battery that Fig. 3 assembles for using embodiment 1 gained blocky graphite negative material
Figure.
Detailed description of the invention
Below in conjunction with detailed description of the invention, the present invention is further illustrated.
In detailed description of the invention, agents useful for same and raw material are commercial goods.
Embodiment 1
The lithium ion battery of the present embodiment blocky graphite negative material, including blocky graphite matrix, described blocky graphite
Matrix surface is coated with graphite coat layer.The D50 of this blocky graphite negative material is 17.36 μm, and tap density is 1.152g/
cm3, specific surface area is 1.526m2/g。
The lithium ion battery of the present embodiment preparation method of blocky graphite negative material, comprises the following steps:
1) choose the blocky graphite that purity is that the 90%th, D50 is 50 μm, select size distribution D50 with pulverizer crushing and classification
It is the blocky graphite particle of 20 μm, blocky graphite, NaOH solid and deionized water are pressed the mass ratio of 1:0.3:0.7 at 550 DEG C
Lower alkali melts 1.5h, washing and after being dried again with 15% hydrochloric acid under 80 DEG C of constant temperature acidleach 2.5h, deionized water cleaning is placed on for 3 times
Vacuum drying oven is warming up to 50 DEG C of dry 10h, obtains the blocky graphite particle that purity is 98.8%, be heated in purifying furnace
3000 DEG C, being incubated 0.5h, obtaining purity with the classification of pulverizer separating twice again after being down to room temperature is 99.98%, and D50 is 17.5 μ
M, tap density is 1.0g/cm3, specific surface area is 5.5m2The blocky graphite matrix of/g；
2) by step 1) pitch of gained blocky graphite matrix and D50≤3 μm presses the mass ratio of 1:0.04 in mixer
After mixing, under nitrogen protection, in airtight kiln, be warming up to 1000 DEG C and be incubated 5h and carry out charing process, after be down to room
Temperature, obtains carbonized material；
3) by step 2) gained carbonized material be placed in the high temperature kiln that temperature is 2700 DEG C insulation 6h carry out graphitization processing,
Removing magnetic treatment with 200 eye mesh screen screenings, degausser again after being down to room temperature, obtaining D50 is 17.36 μm, and tap density is 1.152g/
cm3, specific surface area is 1.526m2The blocky graphite negative material of/g.
The present embodiment gained blocky graphite negative material is conventionally made cathode pole piece, particularly as follows: by carboxylic first
Base sodium cellulosate (CMC) and deionized water are stirred by the mass ratio of 3:200, the superconduction adding mass fraction to be 1%
Carbon black (SP) simultaneously stirs, and adds the blocky graphite powder of 95.3% and mixes 2h, being eventually adding the Carboxy of 2.2%
Latex (SBR), after it mixes, being diluted to solid content by deionized water is 45%.With coating machine by above-mentioned prepared slurry
Material is coated uniformly on totally smooth Copper Foil, to be dried after carry out roll-in to pole piece with roll squeezer again, i.e. can get negative pole pole
Piece.Detect its bounce-back, expansion character testing result as shown in Figure 1.It will be seen from figure 1 that the bounce-back when 4.2V for the cathode pole piece,
It is expanded to 21.25%；The pole piece bounce-back of blocky graphite negative material before full electricity is respectively less than 22%, and at following cycle 100 to 500
Zhou Shi, bounce-back is stable in the range of 22%～27%.
The present embodiment gained blocky graphite negative material is made negative pole, and metal lithium sheet is made, to electrode, to use 1MLiPF6+
EC:EMC:DEC=1:1:1 system electrolyte, 25 μ m-thick lithium ion battery PE/PP/PE barrier films, prepare half-cell.After test
Going out this half-cell gram volume that discharges first is 370.3mAh/g, and coulombic efficiency is up to 92.5% first.
The present embodiment gained blocky graphite negative material is made negative pole, LiCoO2Make positive pole, use 1MLiPF6+EC:
EMC:DEC=1:1:1 system electrolyte, 25 μ m-thick lithium ion battery PE/PP/PE barrier films, prepare full battery.To this full battery
First charge-discharge and cycle performance detect, and result is as shown in Figure 2,3.
Figure it is seen that the full battery of lithium ion with the present embodiment gained blocky graphite material as negative pole discharges first
Capacity is up to 1041.5mAh.This full battery with the capacity that 2C, 5C, 6C discharge be respectively 1C discharge capacity the 99.1%th,
99.6%th, 99.1%, and from figure 3, it can be seen that in whole 500 cyclic processes its capacitance loss rate be below 12%, 1C fills
Electric discharge capability retention after 500 charge and discharge cycles is maintained at 88.5%.
Embodiment 2
The lithium ion battery of the present embodiment blocky graphite negative material, including blocky graphite matrix, described blocky graphite
Matrix surface is coated with graphite coat layer.The D50 of this blocky graphite negative material is 14.36 μm, and tap density is 1.023g/
cm3, specific surface area is 1.952m2/g。
The lithium ion battery of the present embodiment preparation method of blocky graphite negative material, comprises the following steps:
1) choose the blocky graphite that purity is that the 80%th, D50 is 70 μm, select size distribution D50 with pulverizer crushing and classification
It is the blocky graphite particle of 25 μm, blocky graphite, NaOH solid and deionized water are pressed the mass ratio of 1:0.4:0.6 at 500 DEG C
Lower alkali melts 2h, and after washing and being dried, acidleach 2h, the deionized water cleaning 4 times under 90 DEG C of constant temperature with 13% hydrochloric acid again, is placed in true
Empty drying oven is warming up to 120 DEG C of dry 3h, obtains the blocky graphite particle that purity is 98.5%, be heated in purifying furnace
2500 DEG C, being incubated 1.0h, obtaining purity with the classification of pulverizer separating twice again after being down to room temperature is 99.95%, and D50 is respectively
17.5 μm, 12.5 μm, 8.5 μm, tap density is respectively 1.0g/cm3、0.9g/cm3、0.8g/cm3, specific surface area is respectively
5.5m2/g、7.5m2/g、9.5m2Blocky graphite matrix B1, B2, B3 of/g；
2) by step 1) gained blocky graphite matrix B1, B2, B3 mix in the ratio of 5:3:2, then with D50≤3 μm
Pitch mix in mixer by the mass ratio of 1:0.05 after, under nitrogen protection, be warming up in airtight kiln
1400 DEG C and be incubated 2h and carry out charing process, after be down to room temperature, obtain carbonized material；
3) by step 2) gained carbonized material be placed in the high temperature kiln that temperature is 2500 DEG C insulation 7h carry out graphitization processing,
Removing magnetic treatment with 250 eye mesh screen screenings, degausser again after being down to room temperature, obtaining D50 is 14.36 μm, and tap density is 1.023g/
cm3, specific surface area is 1.952m2The blocky graphite negative material of/g.
The present embodiment gained blocky graphite negative material is used to prepare cathode pole piece, lithium ion battery half-cell and full battery
And its performance is detected, preparation and detection method are with embodiment 1.
Testing result: the bounce-back when 4.2V for the cathode pole piece, be expanded to 20.02%.Draw after half-cell test and put first
Electricity gram volume is 371.6mAh/g, and coulombic efficiency is up to 92.1% first.With the capacity of 2C, 5C, 6C electric discharge after full battery testing
It is the 99.4%th, the 99.2%th, the 99.3% of 1C discharge capacity respectively, and with 500 weeks capability retentions of 1C discharge and recharge 87.6%.
Embodiment 3
The lithium ion battery of the present embodiment blocky graphite negative material, including blocky graphite matrix, described blocky graphite
Matrix surface is coated with graphite coat layer.The D50 of this blocky graphite negative material is 14.66 μm, and tap density is 1.146g/
cm3, specific surface area is 2.058m2/g。
The lithium ion battery of the present embodiment preparation method of blocky graphite negative material, comprises the following steps:
1) choose the blocky graphite that purity is that the 85%th, D50 is 100 μm, select size distribution D50 with pulverizer crushing and classification
It is the blocky graphite particle of 30 μm, blocky graphite, NaOH solid and deionized water are pressed the mass ratio of 1:0.3:0.7 at 550 DEG C
Lower alkali melts 1.5h, washing and after being dried again with 15% hydrochloric acid under 80 DEG C of constant temperature acidleach 2.5h, deionized water cleaning 2 times, juxtaposition
It is warming up to 100 DEG C of dry 5h in vacuum drying oven, obtains the blocky graphite particle that purity is 98.7%, heat in purifying furnace
To 2000 DEG C, being incubated 1.5h, obtaining purity with the classification of pulverizer separating twice again after being down to room temperature is 99.97%, and D50 is respectively
17.5 μm, 12.5 μm, 8.5 μm, tap density is respectively 1.0g/cm3、0.9g/cm3、0.8g/cm3, specific surface area is respectively
5.5m2/g、7.5m2/g、9.5m2Blocky graphite matrix C1, C2, C3 of/g；
2) by step 1) gained blocky graphite matrix C1, C2, C3 mix in the ratio of 5:3:2, then with D50≤3 μm
Furane resins mix in mixer by the mass ratio of 1:0.06 after, under nitrogen protection, in airtight kiln heat up
To 1100 DEG C and be incubated 5h and carry out charing process, after be down to room temperature, obtain carbonized material；
3) by step 2) gained carbonized material be placed in the high temperature kiln that temperature is 3000 DEG C insulation 5h carry out graphitization processing,
Removing magnetic treatment with 250 eye mesh screen screenings, degausser again after being down to room temperature, obtaining D50 is 14.66 μm, and tap density is 1.146g/
cm3, specific surface area is 2.058m2The blocky graphite negative material of/g.
The present embodiment gained blocky graphite negative material is used to prepare cathode pole piece, lithium ion battery half-cell and full battery
And its performance is detected, preparation and detection method are with embodiment 1.
Testing result: the bounce-back when 4.2V for the cathode pole piece, be expanded to 22.45%.Draw after half-cell test and put first
Electricity gram volume is 372.8mAh/g, and coulombic efficiency is up to 91.9% first.With the capacity of 2C, 5C, 6C electric discharge after full battery testing
It is the 98.6%th, the 98.5%th, the 98.9% of 1C discharge capacity respectively, and with 500 weeks capability retentions of 1C discharge and recharge 87.2%.
Embodiment 4
The lithium ion battery of the present embodiment blocky graphite negative material, including blocky graphite matrix, described blocky graphite
Matrix surface is coated with graphite coat layer.The D50 of this blocky graphite negative material is 17.65 μm, and tap density is 1.052g/
cm3, specific surface area is 1.415m2/g。
The lithium ion battery of the present embodiment preparation method of blocky graphite negative material, comprises the following steps:
1) choose the blocky graphite that purity is that the 95%th, D50 is 60 μm, select size distribution D50 with pulverizer crushing and classification
It is the blocky graphite particle of 20 μm, blocky graphite, NaOH solid and deionized water are pressed the mass ratio of 1:0.2:0.8 at 600 DEG C
Lower alkali melts 1h, and after washing and being dried, acidleach 3h, the deionized water cleaning 1 time under 70 DEG C of constant temperature with 17% hydrochloric acid again, is placed in true
Empty drying oven is warming up to 60 DEG C of dry 8h, obtains the blocky graphite particle that purity is 99.0%, be heated in purifying furnace
2800 DEG C, being incubated 1.0h, obtaining purity with the classification of pulverizer separating twice again after being down to room temperature is 99.99%, and D50 is 17.5 μ
M, tap density is 1.0g/cm3, specific surface area is 5.5m2The blocky graphite matrix of/g；
2) by step 1) gained blocky graphite matrix mixing by the mass ratio of 1:0.03 with the furane resins of D50≤3 μm
After machine mixes, under nitrogen protection, it in airtight kiln, is warming up to 1300 DEG C and is incubated 3h and carries out charing process, dropping afterwards
To room temperature, obtain carbonized material；
3) by step 2) gained carbonized material be placed in the high temperature kiln that temperature is 2600 DEG C insulation 7h carry out graphitization processing,
Removing magnetic treatment with 200 eye mesh screen screenings, degausser again after being down to room temperature, obtaining D50 is 17.56 μm, and tap density is 1.052g/
cm3, specific surface area is 1.415m2The blocky graphite negative material of/g.
The present embodiment gained blocky graphite negative material is used to prepare cathode pole piece, lithium ion battery half-cell and full battery
And its performance is detected, preparation and detection method are with embodiment 1.
Testing result: the bounce-back when 4.2V for the cathode pole piece, be expanded to 22.65%.Draw after half-cell test and put first
Electricity gram volume is 370.3mAh/g, and coulombic efficiency is up to 91.3% first.With the capacity of 2C, 5C, 6C electric discharge after full battery testing
It is the 98.4%th, the 99.3%th, the 99.2% of 1C discharge capacity respectively, and with 500 weeks capability retentions of 1C discharge and recharge 87.8%.
Embodiment 5
The lithium ion battery of the present embodiment blocky graphite negative material, including blocky graphite matrix, described blocky graphite
Matrix surface is coated with graphite coat layer.The D50 of this blocky graphite negative material is 14.39 μm, and tap density is 1.169g/
cm3, specific surface area is 1.998m2/g。
The lithium ion battery of the present embodiment preparation method of blocky graphite negative material, comprises the following steps:
1) choose the blocky graphite that purity is that the 92%th, D50 is 90 μm, select size distribution D50 with pulverizer crushing and classification
It is the blocky graphite particle of 25 μm, blocky graphite, NaOH solid and deionized water are pressed the mass ratio of 1:0.2:0.8 at 600 DEG C
Lower alkali melts 1h, and after washing and being dried, acidleach 3h, the deionized water cleaning 4 times under 70 DEG C of constant temperature with 17% hydrochloric acid again, is placed in true
Empty drying oven is warming up to 80 DEG C of dry 6h, obtains the blocky graphite particle that purity is 98.9%, be heated in purifying furnace
2300 DEG C, being incubated 1.0h, obtaining purity with the classification of pulverizer separating twice again after being down to room temperature is 99.96%, and D50 is respectively
17.5 μm, 12.5 μm, 8.5 μm, tap density is respectively 1.0g/cm3、0.9g/cm3、0.8g/cm3, specific surface area is respectively
5.5m2/g、7.5m2/g、9.5m2Blocky graphite matrix E1, E2, E3 of/g；
2) by step 1) the EAA resin of gained blocky graphite matrix and D50≤3 μm presses the mass ratio of 1:0.04 at mixer
In mix after, under nitrogen protection, in airtight kiln, be warming up to 1200 DEG C and be incubated 3h and carry out charing process, after be down to
Room temperature, obtains carbonized material；
3) by step 2) gained carbonized material be placed in the high temperature kiln that temperature is 2800 DEG C insulation 6h carry out graphitization processing,
Removing magnetic treatment with 250 eye mesh screen screenings, degausser again after being down to room temperature, obtaining D50 is 14.39 μm, and tap density is 1.169g/
cm3, specific surface area is 1.998m2The blocky graphite negative material of/g.
The present embodiment gained blocky graphite negative material is used to prepare cathode pole piece, lithium ion battery half-cell and full battery
And its performance is detected, preparation and detection method are with embodiment 1.
Testing result: the bounce-back when 4.2V for the cathode pole piece, be expanded to 21.69%.Draw after half-cell test and put first
Electricity gram volume is 369.6mAh/g, and coulombic efficiency is up to 91.8% first.With the capacity of 2C, 5C, 6C electric discharge after full battery testing
It is the 99.0%th, the 99.8%th, the 99.4% of 1C discharge capacity respectively, and with 500 weeks capability retentions of 1C discharge and recharge 87.7%.
Embodiment 6
The lithium ion battery of the present embodiment blocky graphite negative material, including blocky graphite matrix, described blocky graphite
Matrix surface is coated with graphite coat layer.The D50 of this blocky graphite negative material is 17.98 μm, and tap density is 1.065g/
cm3, specific surface area is 1.369m2/g。
The lithium ion battery of the present embodiment preparation method of blocky graphite negative material, comprises the following steps:
1) choose the blocky graphite that purity is that the 83%th, D50 is 80 μm, select size distribution D50 with pulverizer crushing and classification
It is the blocky graphite particle of 27 μm, blocky graphite, NaOH solid and deionized water are pressed the mass ratio of 1:0.4:0.6 at 500 DEG C
Lower alkali melts 2h, and after washing and being dried, acidleach 2h, the deionized water cleaning 3 times under 90 DEG C of constant temperature with 13% hydrochloric acid again, is placed in true
Empty drying oven is warming up to 70 DEG C of dry 8h, obtains the blocky graphite particle that purity is 98.6%, be heated in purifying furnace
2200 DEG C, being incubated 1.5h, obtaining purity with the classification of pulverizer separating twice again after being down to room temperature is 99.95%, and D50 is 17.5 μ
M, tap density is 1.0g/cm3, specific surface area is respectively 5.5m2The blocky graphite matrix of/g；
2) by step 1) the EAA resin of gained blocky graphite matrix and D50≤3 μm presses the mass ratio of 1:0.03 at mixer
In mix after, under nitrogen protection, in airtight kiln, be warming up to 1100 DEG C and be incubated 4h and carry out charing process, after be down to
Room temperature, obtains carbonized material；
3) by step 2) gained carbonized material be placed in the high temperature kiln that temperature is 2900 DEG C insulation 5h carry out graphitization processing,
Removing magnetic treatment with 200 eye mesh screen screenings, degausser again after being down to room temperature, obtaining D50 is 17.98 μm, and tap density is 1.065g/
cm3, specific surface area is 1.369m2The blocky graphite negative material of/g.
The present embodiment gained blocky graphite negative material is used to prepare cathode pole piece, lithium ion battery half-cell and full battery
And its performance is detected, preparation and detection method are with embodiment 1.
Testing result: the bounce-back when 4.2V for the cathode pole piece, be expanded to 21.97%.Draw after half-cell test and put first
Electricity gram volume is 372.6mAh/g, and coulombic efficiency is up to 92.0% first.With the capacity of 2C, 5C, 6C electric discharge after full battery testing
It is the 98.9%th, the 99.4%th, the 99.2% of 1C discharge capacity respectively, and with 500 weeks capability retentions of 1C discharge and recharge 87.6%.
Experimental example
The physical property to embodiment 1～6 gained blocky graphite negative material for this experimental example detects, result such as table 1
Shown in.
Wherein, comparative example 1 is to change the blocky graphite in embodiment 1 into natural flake graphite, and remaining is by the side of embodiment 1
Method process, obtaining D50 is 17.96 μm, and tap density is 1.175g/cm3, specific surface area is 1.898m2The natural flake graphite of/g
Negative material.According to method same as in Example 1, this natural flake graphite negative material is made cathode pole piece, and assembles
Become lithium ion battery half-cell and full battery.Testing result: the bounce-back when 4.2V for the cathode pole piece, be expanded to 31.53%；Half electricity
Showing that discharge capacity is 366.9mAh/g first after the test of pond, coulombic efficiency is up to 91.4% first；With 2C after full battery testing
The capacity of electric discharge is the 96.1% of 1C discharge capacity, and with 500 weeks capability retentions of 1C discharge and recharge 79.2%.
Comparative example 2 is to change the blocky graphite in embodiment 1 into Delanium, and remaining is processed as described in Example 1,
Being 14.58 μm to D50, tap density is 1.098g/cm3, specific surface area is 1.658m2The artificial plumbago negative pole material of/g.According to
This artificial plumbago negative pole material is made cathode pole piece, and is assembled into lithium ion battery half-cell by method same as in Example 1
With full battery.Testing result: the bounce-back when 4.2V for the cathode pole piece, be expanded to 17.56%；Draw after half-cell test and put first
Electricity gram volume is 346.1mAh/g, and coulombic efficiency is up to 92.1% first；With the capacity of 2C, 5C, 6C electric discharge after full battery testing
It is the 98.8%th, the 98.0%th, the 98.4% of 1C discharge capacity respectively, and with 500 weeks capability retentions of 1C discharge and recharge 85.7%.
The physical property testing result of table 1 embodiment 1～6 gained blocky graphite negative material
Lithium ion battery half-cell, the chemical property of full battery that embodiment 1～6 is assembled by this experimental example are examined
Surveying, testing result is as shown in table 2.
The chemical property testing result of the full battery of lithium ion battery half-cell that table 2 embodiment 1～6 assembles
From table 2 it can be seen that use lithium ion battery half electricity that embodiment 1～6 gained blocky graphite negative material assembles
The high rate performance that the gram volume of electric discharge first in pond is above under natural flake graphite and Delanium, and big electric current is excellent compared with comparative example
Show, the capacity with 2C, 5C, 6C electric discharge is more than the 98% of 1C discharge capacity respectively；In addition, under 1C multiplying power discharge and recharge 500 weeks
Capability retention all big than the capability retention of comparative example.Test result indicate that, the blocky graphite negative material of the present invention can
Being applied to field of lithium ion battery as a kind of new negative material, and there is excellent chemical property.
This experimental example is also to using the bounce-back of the cathode pole piece prepared of embodiment 1～6 gained blocky graphite negative material, swollen
Swollen performance detects, and testing result is as shown in table 3.
The bounce-back of cathode pole piece prepared by table 3 embodiment 1～6 gained blocky graphite negative material, expansion character detection knot
Really
From table 3 it can be seen that use the bounce-back of the cathode pole piece prepared of embodiment 1～6 gained blocky graphite negative material,
Expand and be respectively less than 23%.Test result indicate that, the bounce-back of cathode pole piece prepared by the blocky graphite negative material of the present invention, expansion
Less.
Claims (7)
1. a lithium ion battery blocky graphite negative material, it is characterised in that: include blocky graphite matrix, described block stone
Ink matrix surface is coated with graphite coat layer；
The D50 of this blocky graphite negative material is 14.36～17.98 μm, and tap density is 1.023～1.169g/cm3, compares table
Area is 1.369～2.058m m2/g；
Described lithium ion battery blocky graphite negative material uses the method comprising the steps to prepare:
1) take after blocky graphite matrix mixes with covering, under protective atmosphere, be warming up to 1000～1400 DEG C and be incubated 2
～5h carries out charing process, after be down to room temperature, obtain carbonized material；
2) by step 1) gained carbonized material is incubated 5～7h under the conditions of 2500～3000 DEG C and carries out graphitization processing, is down to room
Wen Houzai is screened, remove magnetic treatment, to obtain final product；
Step 1) described in the mass ratio of blocky graphite matrix and covering be 1:0.03～0.06；
Described covering is furane resins or ethene-ethyl acrylate resin.
2. the preparation method of a lithium ion battery blocky graphite negative material as claimed in claim 1, it is characterised in that:
Comprise the following steps:
1) take after blocky graphite matrix mixes with covering, under protective atmosphere, be warming up to 1000～1400 DEG C and be incubated 2
～5h carries out charing process, after be down to room temperature, obtain carbonized material；
2) by step 1) gained carbonized material is incubated 5～7h under the conditions of 2500～3000 DEG C and carries out graphitization processing, is down to room
Wen Houzai is screened, remove magnetic treatment, to obtain final product；
Step 1) described in the mass ratio of blocky graphite matrix and covering be 1:0.03～0.06；
Described covering is furane resins or ethene-ethyl acrylate resin.
3. the preparation method of lithium ion battery blocky graphite negative material according to claim 2, it is characterised in that:
Step 1) in, the purity of described blocky graphite matrix is 99.95%～99.99%, and D50 is 8.5～17.5 μm, tap density
It is 0.8～1.0g/cm3, specific surface area is 5.5～9.5m2/g。
4. the preparation method of lithium ion battery blocky graphite negative material according to claim 3, it is characterised in that: institute
State blocky graphite matrix to be prepared by following methods:
Take blocky graphite particle, pulverize, use after alkali acid system carries out chemical purification, cleaned, be dried after, high temperature purification, be down to
After room temperature, secondary smashes and i.e. obtains blocky graphite matrix again.
5. the preparation method of lithium ion battery blocky graphite negative material according to claim 4, it is characterised in that:
Described alkali acid system be by blocky graphite, NaOH solid and deionized water by the mass ratio of 1:0.2～0.4:0.6～0.8 500
At～600 DEG C, alkali melts 1～2h, washing and after being dried again with the hydrochloric acid that concentration is 13%～17% under the conditions of 70～90 DEG C constant temperature
Acidleach 2～3h, finally washing is simultaneously dried.
6. the preparation method of lithium ion battery blocky graphite negative material according to claim 4, it is characterised in that: institute
Stating high temperature purification is insulation 0.5～1.5h under the conditions of 2000～3000 DEG C.
7. a lithium ion battery, it is characterised in that: use the blocky graphite negative material described in claim 1 as negative pole material
Material.
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| CN108101539A (en) * | 2017-12-20 | 2018-06-01 | 徐会丽 | A kind of blocky graphite base negative material and its preparation method and application |
| CN108123135B (en) * | 2017-12-20 | 2020-05-19 | 内蒙古瑞盛炭素新材料科技有限公司 | Cathode material adopting blocky graphite and preparation method and application thereof |
| CN108117072A (en) * | 2017-12-20 | 2018-06-05 | 徐会丽 | A kind of modified blocky graphite material and its preparation method and application |
| CN108134086A (en) * | 2017-12-23 | 2018-06-08 | 瀛ｅ姜 | A kind of graphite material for improving charging and discharging capacity and its preparation method and application |
| CN108172832A (en) * | 2017-12-23 | 2018-06-15 | 瀛ｅ姜 | A kind of graphite material of stabilization and its preparation method and application |
| CN108155380A (en) * | 2017-12-23 | 2018-06-12 | 郑州源冉生物技术有限公司 | A kind of blocky graphite material of low bulk and its preparation method and application |
| CN108163849A (en) * | 2017-12-23 | 2018-06-15 | 瀛ｅ姜 | A kind of highly conductive graphite material and its preparation method and application |
| CN108706582A (en) * | 2018-06-27 | 2018-10-26 | 河南易成新能源股份有限公司 | The preparation method of artificial plumbago negative pole material |
| CN110880600B (en) * | 2019-11-21 | 2021-09-07 | 广东东岛新能源股份有限公司 | Negative electrode material with high temperature resistance, preparation method thereof and application thereof in lithium ion battery |
| CN113104845B (en) * | 2020-01-13 | 2022-07-29 | 上海昱瓴新能源科技有限公司 | Method for preparing porous artificial graphite cathode material by using electrode joint powder as raw material |
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