CN104393298A - Blocky graphite negative electrode material for lithium ion battery, preparation method of blocky graphite negative electrode material and lithium ion battery - Google Patents
Blocky graphite negative electrode material for lithium ion battery, preparation method of blocky graphite negative electrode material and lithium ion battery Download PDFInfo
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- CN104393298A CN104393298A CN201410556821.3A CN201410556821A CN104393298A CN 104393298 A CN104393298 A CN 104393298A CN 201410556821 A CN201410556821 A CN 201410556821A CN 104393298 A CN104393298 A CN 104393298A
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Abstract
The invention discloses a blocky graphite negative electrode material for a lithium ion battery, a preparation method of the blocky graphite negative electrode material and the lithium ion battery. The negative electrode material comprises a blocky graphite matrix, wherein the surface of the blocky graphite matrix is coated with a graphite coating layer. According to the blocky graphite negative electrode material for the lithium ion battery, a great number of micro-holes are formed in the surface of the blocky graphite matrix, and the graphite coating layer is highly combined with the coated blocky graphite matrix, so that the blocky graphite negative electrode material has the advantages of high intermolecular binding force, high tap density, high reversible specific capacity and good rate performance, a negative electrode sheet prepared by using the blocky graphite negative electrode material is slightly bounced and expanded, and the prepared lithium ion battery has excellent electrochemical performance. According to the blocky graphite negative electrode material, the purpose of blocky graphite is expanded, the additional value of a natural graphite product is increased, and the development space of a negative electrode material source of the lithium ion battery is enlarged; the negative electrode material can be used as the negative electrode material of an aluminum shell lithium ion battery, a flexibly package lithium ion battery, a cylindrical lithium ion battery and other lithium ion batteries; the blocky graphite negative electrode material has a wide application prospect.
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 material, also relate to a kind of preparation method of lithium ion battery blocky graphite negative material simultaneously and use the lithium ion battery of this blocky graphite negative material.
Background technology
Compared with traditional plumbic acid, NI-G secondary cell, the advantages such as lithium ion battery has that operating voltage is high, specific energy is high, operating temperature range is wide, electric discharge is steady, has extended cycle life, memory-less effect, therefore it is widely used in the fields such as communication equipment, electric tool, Aero-Space as a kind of novel energy-storing power supply.At present, along with the continuous progress of technology, people have higher requirement to lithium ion battery, and the lithium ion battery with performances such as high-energy-density, high rate capability, long circulation life, high safety factors becomes the study hotspot of people gradually.
As one of lithium ion battery critical material, negative material enjoys the concern of people always.Lithium ion battery negative material need meet following characteristics: 1) oxidation-reduction potential is close to lithium current potential; 2) lithium ion inserts and deviate from should be reversible; 3) lithium ion diffusion coefficient in material of main part is large; 4) in charge and discharge process, agent structure is stablized; 5) electronics and ionic conductivity high; 6) low price, pollution-free.In current material, graphite becomes the main flow of lithium ion battery negative material because of features such as it is with low cost, good processability, good conductivity, stable performances.
Native graphite is very abundant at China's reserves, cheap, and degree of crystallinity is high, is to produce one of upper widely used negative material at present.Different according to crystal habit, native graphite can be divided into compact crystal shape graphite, crystalline flake graphite, aphanitic graphite three class, and wherein compact crystal shape graphite is also known as making blocky graphite, and this graphite is formed by pneumatolysis.Blocky graphite grade is very high, 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.At present, researcher has mainly carried out large quantity research to crystalline flake graphite as lithium ion battery negative material, and blocky graphite then rarely has research.Therefore, for expanding the purposes of blocky graphite, expanding the development space in lithium ion battery negative material source, developing one of a kind of blocky graphite negative material important research direction becoming lithium ion battery.
Summary of the invention
The object of this invention is to provide a kind of lithium ion battery blocky graphite negative material.
Second object of the present invention is to provide a kind of preparation method of lithium ion battery blocky graphite negative material.
3rd 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 above object, the technical solution adopted in the present invention is: a kind of lithium ion battery blocky graphite negative material, comprises blocky graphite matrix, and 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/cm
3, specific area is 1.1 ~ 2.4m
2/ g.
A preparation method for above-mentioned lithium ion battery blocky graphite negative material, comprises the following steps:
1) get after blocky graphite 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, after be down to room temperature, obtain carbonized material;
2) by step 1) gained carbonized material is incubated 5 ~ 7h and carries out graphitization processing under 2500 ~ 3000 DEG C of conditions, again through screening, except magnetic treatment, to obtain final product after being down to room temperature.
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%, D50 is 8.5 ~ 17.5 μm, and tap density is 0.8 ~ 1.0g/cm
3, specific area is 5.5 ~ 9.5m
2/ g.
Described blocky graphite matrix is prepared by following methods:
Get blocky graphite particle, pulverize, after adopting alkali acid system to carry out chemical purification, after cleaning, drying, high temperature purification, after being down to room temperature, secondary shatters and obtains blocky graphite matrix again.
Described blocky graphite matrix can be mixed by the blocky graphite particle that D50 is different.
80% ~ 95%, D50 of described blocky graphite particle is 25 ~ 100 μm.
Described pulverizing refers to that pulverizing also classification selects the particle that D50 is 20 ~ 30 μm.
Described alkali acid system is that blocky graphite, NaOH solid and deionized water are melted 1 ~ 2h by mass ratio alkali at 500 ~ 600 DEG C of 1:0.2 ~ 0.4:0.6 ~ 0.8, washing and drying after again with hydrochloric acid constant temperature acidleach 2 ~ 3h under 70 ~ 90 DEG C of conditions that concentration is 13% ~ 17%, finally washing and drying.
Washed with de-ionized water 1 ~ 4 time is used in described cleaning.
Described drying is dry 3 ~ 10h under 50 ~ 120 DEG C of conditions.
Described high temperature purification is incubated 0.5 ~ 1.5h under 2000 ~ 3000 DEG C of conditions.
Described secondary shatters and refers to that pulverizing also classification selects 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, adopts above-mentioned blocky graphite negative material as negative material.
Lithium ion battery blocky graphite negative material of the present invention, 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 increase the contact area of covering and matrix greatly, add the tightness of binder course, make the structure of end product blocky graphite more fine and close; After coated, the associativity of graphite coat layer and blocky graphite matrix is good, blocky graphite negative material is had, and inter-molecular binding force is strong, tap density is high, reversible specific capacity is high, the advantage of good rate capability, the negative plate adopting this blocky graphite negative material to prepare rebounds, it is little to expand, the lithium ion battery of preparation has good chemical property, meets the requirement of people for lithium ion battery high-energy-density, high rate capability, long circulation life, 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 the negative material of the lithium ion batteries such as aluminum hull, Soft Roll and cylinder, has broad application prospects.
The preparation method of lithium ion battery blocky graphite negative material of the present invention, after blocky graphite matrix is mixed with covering, pulverize again after charing, graphitization processing, sieve, except magnetic, gained blocky graphite negative material has good chemical property, can improve the reversible specific capacity of lithium ion battery, efficiency for charge-discharge, stable cycle performance and high rate performance; This preparation method's technique is simple, easy to operate, and raw material sources are extensive, and cost is low, is applicable to large-scale industrial production.
Further, blocky graphite matrix be by blocky graphite raw material through shattering, chemical purification, washing, drying, screening, again after high temperature secondary is purified, the purity obtained is the blocky graphite particle of 99.95% ~ 99.99%, high temperature purification makes graphite purity be improved on the one hand, make the further graphitization of graphite on the other hand, thus improve the degree of graphitization of blocky graphite, thus improve the quality of blocky graphite matrix.
Accompanying drawing explanation
Fig. 1 is bounce-back, the expansion curve figure of the negative plate that embodiment 1 gained blocky graphite negative material is made.
Fig. 2 is the discharge curve first of the full battery of lithium ion battery adopting the assembling of embodiment 1 gained blocky graphite negative material;
Fig. 3 is the cyclic curve figure of the full battery of lithium ion battery adopting the assembling of embodiment 1 gained blocky graphite negative material.
Embodiment
Below in conjunction with embodiment, the present invention is further illustrated.
In embodiment, agents useful for same and raw material are commercial goods.
Embodiment 1
The lithium ion battery blocky graphite negative material of the present embodiment, comprises blocky graphite matrix, and 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/cm
3, specific area is 1.526m
2/ g.
The lithium ion battery preparation method of blocky graphite negative material of the present embodiment, comprises the following steps:
1) choosing purity is 90%, D50 is the blocky graphite of 50 μm, the blocky graphite particle that particle size distribution D50 is 20 μm is selected with pulverizer crushing and classification, by blocky graphite, NaOH solid and deionized water melt 1.5h by mass ratio alkali at 550 DEG C of 1:0.3:0.7, 15% hydrochloric acid acidleach 2.5h under 80 DEG C of constant temperature is used again after washing and drying, washed with de-ionized water is placed in vacuum drying oven for 3 times and is warming up to 50 DEG C of dry 10h, obtain the blocky graphite particle that purity is 98.8%, 3000 DEG C are heated in purifying furnace, insulation 0.5h, obtaining purity with the classification of pulverizer separating twice again after being down to room temperature is 99.98%, D50 is 17.5 μm, tap density is 1.0g/cm
3, specific area is 5.5m
2the blocky graphite matrix of/g,
2) by step 1) after the pitch of gained blocky graphite matrix and D50≤3 μm mixes in mixer by the mass ratio of 1:0.04, under nitrogen protection, in airtight kiln, be warming up to 1000 DEG C and be incubated 5h carry out charing process, after be down to room temperature, obtain carbonized material;
3) by step 2) to be placed in temperature be that the high temperature kiln of 2700 DEG C is incubated 6h and carries out graphitization processing to gained carbonized material, to be down to after room temperature again with 200 eye mesh screens screenings, degausser except magnetic treatment, obtaining D50 is 17.36 μm, and tap density is 1.152g/cm
3, specific area is 1.526m
2the blocky graphite negative material of/g.
The present embodiment gained blocky graphite negative material is conventionally made cathode pole piece, be specially: sodium carboxymethylcellulose (CMC) and deionized water are stirred by the mass ratio of 3:200, add mass fraction be the superconduction carbon black (SP) of 1% and stir, add the blocky graphite powder of 95.3% again and mix 2h, finally add the carboxylic styrene butadiene latex (SBR) of 2.2%, after it mixes, being diluted to solid content with deionized water is 45%.With coating machine, above-mentioned obtained slurry is evenly coated on totally smooth Copper Foil, with roll squeezer, roll-in is carried out to pole piece again after to be dried, can cathode pole piece be obtained.Detect its bounce-back, expansion character testing result as shown in Figure 1.As can be seen from Figure 1, the bounce-back of cathode pole piece when 4.2V, 21.25% is expanded to; Before full electricity, the pole piece bounce-back of blocky graphite negative material is all less than 22%, and when following cycle 100 to 500 week, bounce-back is stabilized in 22% ~ 27% scope.
The present embodiment gained blocky graphite negative material is made negative pole, and metal lithium sheet is done electrode, adopts 1MLiPF
6+ EC:EMC:DEC=1:1:1 system electrolyte, 25 μm of thick lithium ion battery PE/PP/PE barrier films, prepare half-cell.Show after test that this half-cell gram volume that discharges first is 370.3mAh/g, coulombic efficiency is up to 92.5% first.
The present embodiment gained blocky graphite negative material is made negative pole, LiCoO
2make positive pole, adopt 1MLiPF
6+ EC:EMC:DEC=1:1:1 system electrolyte, 25 μm of thick lithium ion battery PE/PP/PE barrier films, prepare full battery.Detect the first charge-discharge of this full battery and cycle performance, result as shown in Figure 2,3.
As can be seen from Figure 2, with the present embodiment gained blocky graphite material full battery of lithium ion that is negative pole first discharge capacity up to 1041.5mAh.This full battery is 99.1%, 99.6%, 99.1% of 1C discharge capacity respectively with the capacity that 2C, 5C, 6C discharge, and as can be seen from Figure 3, in whole 500 cyclic processes, its capacitance loss rate all remains on 88.5% lower than 12%, 1C discharge and recharge capability retention after 500 charge and discharge cycles.
Embodiment 2
The lithium ion battery blocky graphite negative material of the present embodiment, comprises blocky graphite matrix, and 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/cm
3, specific area is 1.952m
2/ g.
The lithium ion battery preparation method of blocky graphite negative material of the present embodiment, comprises the following steps:
1) choosing purity is 80%, D50 is the blocky graphite of 70 μm, the blocky graphite particle that particle size distribution D50 is 25 μm is selected with pulverizer crushing and classification, by blocky graphite, NaOH solid and deionized water melt 2h by mass ratio alkali at 500 DEG C of 1:0.4:0.6, 13% hydrochloric acid acidleach 2h under 90 DEG C of constant temperature is used again after washing and drying, washed with de-ionized water 4 times, and be placed in vacuum drying oven and be warming up to 120 DEG C of dry 3h, obtain the blocky graphite particle that purity is 98.5%, 2500 DEG C are heated in purifying furnace, insulation 1.0h, obtaining purity with the classification of pulverizer separating twice again after being down to room temperature is 99.95%, D50 is respectively 17.5 μm, 12.5 μm, 8.5 μm, tap density is respectively 1.0g/cm
3, 0.9g/cm
3, 0.8g/cm
3, specific area is respectively 5.5m
2/ g, 7.5m
2/ g, 9.5m
2blocky 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, after mixing in mixer by the mass ratio of 1:0.05 with the pitch of D50≤3 μm again, under nitrogen protection, in airtight kiln, be warming up to 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) to be placed in temperature be that the high temperature kiln of 2500 DEG C is incubated 7h and carries out graphitization processing to gained carbonized material, to be down to after room temperature again with 250 eye mesh screens screenings, degausser except magnetic treatment, obtaining D50 is 14.36 μm, and tap density is 1.023g/cm
3, specific area is 1.952m
2the blocky graphite negative material of/g.
Adopt the present embodiment gained blocky graphite negative material prepare cathode pole piece, lithium ion battery half-cell and full battery and detect its performance, preparation and detection method are with embodiment 1.
Testing result: the bounce-back of cathode pole piece when 4.2V, be expanded to 20.02%.Show after half-cell test that the gram volume that discharges first is 371.6mAh/g, coulombic efficiency is up to 92.1% first.The capacity discharged with 2C, 5C, 6C after full battery testing is 99.4%, 99.2%, 99.3% of 1C discharge capacity respectively, and with 1C discharge and recharge 500 weeks capability retentions 87.6%.
Embodiment 3
The lithium ion battery blocky graphite negative material of the present embodiment, comprises blocky graphite matrix, and 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/cm
3, specific area is 2.058m
2/ g.
The lithium ion battery preparation method of blocky graphite negative material of the present embodiment, comprises the following steps:
1) choosing purity is 85%, D50 is the blocky graphite of 100 μm, the blocky graphite particle that particle size distribution D50 is 30 μm is selected with pulverizer crushing and classification, by blocky graphite, NaOH solid and deionized water melt 1.5h by mass ratio alkali at 550 DEG C of 1:0.3:0.7, 15% hydrochloric acid acidleach 2.5h under 80 DEG C of constant temperature is used again after washing and drying, washed with de-ionized water 2 times, and be placed in vacuum drying oven and be warming up to 100 DEG C of dry 5h, obtain the blocky graphite particle that purity is 98.7%, 2000 DEG C are heated in purifying furnace, insulation 1.5h, obtaining purity with the classification of pulverizer separating twice again after being down to room temperature is 99.97%, D50 is respectively 17.5 μm, 12.5 μm, 8.5 μm, tap density is respectively 1.0g/cm
3, 0.9g/cm
3, 0.8g/cm
3, specific area is respectively 5.5m
2/ g, 7.5m
2/ g, 9.5m
2blocky 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, after mixing in mixer by the mass ratio of 1:0.06 with the furane resins of D50≤3 μm again, under nitrogen protection, in airtight kiln, be warming 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) to be placed in temperature be that the high temperature kiln of 3000 DEG C is incubated 5h and carries out graphitization processing to gained carbonized material, to be down to after room temperature again with 250 eye mesh screens screenings, degausser except magnetic treatment, obtaining D50 is 14.66 μm, and tap density is 1.146g/cm
3, specific area is 2.058m
2the blocky graphite negative material of/g.
Adopt the present embodiment gained blocky graphite negative material prepare cathode pole piece, lithium ion battery half-cell and full battery and detect its performance, preparation and detection method are with embodiment 1.
Testing result: the bounce-back of cathode pole piece when 4.2V, be expanded to 22.45%.Show after half-cell test that the gram volume that discharges first is 372.8mAh/g, coulombic efficiency is up to 91.9% first.The capacity discharged with 2C, 5C, 6C after full battery testing is 98.6%, 98.5%, 98.9% of 1C discharge capacity respectively, and with 1C discharge and recharge 500 weeks capability retentions 87.2%.
Embodiment 4
The lithium ion battery blocky graphite negative material of the present embodiment, comprises blocky graphite matrix, and 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/cm
3, specific area is 1.415m
2/ g.
The lithium ion battery preparation method of blocky graphite negative material of the present embodiment, comprises the following steps:
1) choosing purity is 95%, D50 is the blocky graphite of 60 μm, the blocky graphite particle that particle size distribution D50 is 20 μm is selected with pulverizer crushing and classification, by blocky graphite, NaOH solid and deionized water melt 1h by mass ratio alkali at 600 DEG C of 1:0.2:0.8, 17% hydrochloric acid acidleach 3h under 70 DEG C of constant temperature is used again after washing and drying, washed with de-ionized water 1 time, and be placed in vacuum drying oven and be warming up to 60 DEG C of dry 8h, obtain the blocky graphite particle that purity is 99.0%, 2800 DEG C are heated in purifying furnace, insulation 1.0h, obtaining purity with the classification of pulverizer separating twice again after being down to room temperature is 99.99%, D50 is 17.5 μm, tap density is 1.0g/cm
3, specific area is 5.5m
2the blocky graphite matrix of/g,
2) by step 1) after the furane resins of gained blocky graphite matrix and D50≤3 μm mix in mixer by the mass ratio of 1:0.03, under nitrogen protection, in airtight kiln, be warming up to 1300 DEG C and be incubated 3h carry out charing process, after be down to room temperature, obtain carbonized material;
3) by step 2) to be placed in temperature be that the high temperature kiln of 2600 DEG C is incubated 7h and carries out graphitization processing to gained carbonized material, to be down to after room temperature again with 200 eye mesh screens screenings, degausser except magnetic treatment, obtaining D50 is 17.56 μm, and tap density is 1.052g/cm
3, specific area is 1.415m
2the blocky graphite negative material of/g.
Adopt the present embodiment gained blocky graphite negative material prepare cathode pole piece, lithium ion battery half-cell and full battery and detect its performance, preparation and detection method are with embodiment 1.
Testing result: the bounce-back of cathode pole piece when 4.2V, be expanded to 22.65%.Show after half-cell test that the gram volume that discharges first is 370.3mAh/g, coulombic efficiency is up to 91.3% first.The capacity discharged with 2C, 5C, 6C after full battery testing is 98.4%, 99.3%, 99.2% of 1C discharge capacity respectively, and with 1C discharge and recharge 500 weeks capability retentions 87.8%.
Embodiment 5
The lithium ion battery blocky graphite negative material of the present embodiment, comprises blocky graphite matrix, and 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/cm
3, specific area is 1.998m
2/ g.
The lithium ion battery preparation method of blocky graphite negative material of the present embodiment, comprises the following steps:
1) choosing purity is 92%, D50 is the blocky graphite of 90 μm, the blocky graphite particle that particle size distribution D50 is 25 μm is selected with pulverizer crushing and classification, by blocky graphite, NaOH solid and deionized water melt 1h by mass ratio alkali at 600 DEG C of 1:0.2:0.8, 17% hydrochloric acid acidleach 3h under 70 DEG C of constant temperature is used again after washing and drying, washed with de-ionized water 4 times, and be placed in vacuum drying oven and be warming up to 80 DEG C of dry 6h, obtain the blocky graphite particle that purity is 98.9%, 2300 DEG C are heated in purifying furnace, insulation 1.0h, obtaining purity with the classification of pulverizer separating twice again after being down to room temperature is 99.96%, D50 is respectively 17.5 μm, 12.5 μm, 8.5 μm, tap density is respectively 1.0g/cm
3, 0.9g/cm
3, 0.8g/cm
3, specific area is respectively 5.5m
2/ g, 7.5m
2/ g, 9.5m
2blocky graphite matrix E1, E2, E3 of/g,
2) by step 1) after the EAA resin of gained blocky graphite matrix and D50≤3 μm mixes in mixer by the mass ratio of 1:0.04, under nitrogen protection, in airtight kiln, be warming up to 1200 DEG C and be incubated 3h carry out charing process, after be down to room temperature, obtain carbonized material;
3) by step 2) to be placed in temperature be that the high temperature kiln of 2800 DEG C is incubated 6h and carries out graphitization processing to gained carbonized material, to be down to after room temperature again with 250 eye mesh screens screenings, degausser except magnetic treatment, obtaining D50 is 14.39 μm, and tap density is 1.169g/cm
3, specific area is 1.998m
2the blocky graphite negative material of/g.
Adopt the present embodiment gained blocky graphite negative material prepare cathode pole piece, lithium ion battery half-cell and full battery and detect its performance, preparation and detection method are with embodiment 1.
Testing result: the bounce-back of cathode pole piece when 4.2V, be expanded to 21.69%.Show after half-cell test that the gram volume that discharges first is 369.6mAh/g, coulombic efficiency is up to 91.8% first.The capacity discharged with 2C, 5C, 6C after full battery testing is 99.0%, 99.8%, 99.4% of 1C discharge capacity respectively, and with 1C discharge and recharge 500 weeks capability retentions 87.7%.
Embodiment 6
The lithium ion battery blocky graphite negative material of the present embodiment, comprises blocky graphite matrix, and 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/cm
3, specific area is 1.369m
2/ g.
The lithium ion battery preparation method of blocky graphite negative material of the present embodiment, comprises the following steps:
1) choosing purity is 83%, D50 is the blocky graphite of 80 μm, the blocky graphite particle that particle size distribution D50 is 27 μm is selected with pulverizer crushing and classification, by blocky graphite, NaOH solid and deionized water melt 2h by mass ratio alkali at 500 DEG C of 1:0.4:0.6, 13% hydrochloric acid acidleach 2h under 90 DEG C of constant temperature is used again after washing and drying, washed with de-ionized water 3 times, and be placed in vacuum drying oven and be warming up to 70 DEG C of dry 8h, obtain the blocky graphite particle that purity is 98.6%, 2200 DEG C are heated in purifying furnace, insulation 1.5h, obtaining purity with the classification of pulverizer separating twice again after being down to room temperature is 99.95%, D50 is 17.5 μm, tap density is 1.0g/cm
3, specific area is respectively 5.5m
2the blocky graphite matrix of/g,
2) by step 1) after the EAA resin of gained blocky graphite matrix and D50≤3 μm mixes in mixer by the mass ratio of 1:0.03, under nitrogen protection, in airtight kiln, be warming up to 1100 DEG C and be incubated 4h carry out charing process, after be down to room temperature, obtain carbonized material;
3) by step 2) to be placed in temperature be that the high temperature kiln of 2900 DEG C is incubated 5h and carries out graphitization processing to gained carbonized material, to be down to after room temperature again with 200 eye mesh screens screenings, degausser except magnetic treatment, obtaining D50 is 17.98 μm, and tap density is 1.065g/cm
3, specific area is 1.369m
2the blocky graphite negative material of/g.
Adopt the present embodiment gained blocky graphite negative material prepare cathode pole piece, lithium ion battery half-cell and full battery and detect its performance, preparation and detection method are with embodiment 1.
Testing result: the bounce-back of cathode pole piece when 4.2V, be expanded to 21.97%.Show after half-cell test that the gram volume that discharges first is 372.6mAh/g, coulombic efficiency is up to 92.0% first.The capacity discharged with 2C, 5C, 6C after full battery testing is 98.9%, 99.4%, 99.2% of 1C discharge capacity respectively, and with 1C discharge and recharge 500 weeks capability retentions 87.6%.
Experimental example
The physical property of this experimental example to embodiment 1 ~ 6 gained blocky graphite negative material detects, and result is as shown in table 1.
Wherein, comparative example 1 changes the blocky graphite in embodiment 1 into natural flake graphite, and all the other are by the method process of embodiment 1, and obtaining D50 is 17.96 μm, and tap density is 1.175g/cm
3, specific area is 1.898m
2the natural flake graphite negative material of/g.According to the method identical with embodiment 1, this natural flake graphite negative material is made cathode pole piece, and be assembled into lithium ion battery half-cell and full battery.Testing result: the bounce-back of cathode pole piece when 4.2V, be expanded to 31.53%; Show that discharge capacity is 366.9mAh/g first after half-cell test, coulombic efficiency is up to 91.4% first; The capacity discharged with 2C after full battery testing is 96.1% of 1C discharge capacity, and with 1C discharge and recharge 500 weeks capability retentions 79.2%.
Comparative example 2 changes the blocky graphite in embodiment 1 into Delanium, and all the other are by the method process of embodiment 1, and obtaining D50 is 14.58 μm, and tap density is 1.098g/cm
3, specific area is 1.658m
2the artificial plumbago negative pole material of/g.According to the method identical with embodiment 1, this artificial plumbago negative pole material is made cathode pole piece, and be assembled into lithium ion battery half-cell and full battery.Testing result: the bounce-back of cathode pole piece when 4.2V, be expanded to 17.56%; Show after half-cell test that the gram volume that discharges first is 346.1mAh/g, coulombic efficiency is up to 92.1% first; The capacity discharged with 2C, 5C, 6C after full battery testing is 98.8%, 98.0%, 98.4% of 1C discharge capacity respectively, and with 1C discharge and recharge 500 weeks capability retentions 85.7%.
The physical property testing result of table 1 embodiment 1 ~ 6 gained blocky graphite negative material
The lithium ion battery half-cell that this experimental example is assembled embodiment 1 ~ 6, the chemical property of full battery detect, and 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 is assembled
As can be seen from Table 2, adopt the gram volume of electric discharge first of the lithium ion battery half-cell of embodiment 1 ~ 6 gained blocky graphite negative material assembling all higher than natural flake graphite and Delanium, and high rate performance under big current is outstanding compared with comparative example, be more than 98% of 1C discharge capacity respectively with the capacity of 2C, 5C, 6C electric discharge; In addition, under 1C multiplying power, the discharge and recharge capability retention of 500 weeks is all large than the capability retention of comparative example.Experimental result shows, blocky graphite negative material of the present invention can be applied to field of lithium ion battery as a kind of new negative material, and has excellent chemical property.
This experimental example also detects the bounce-back of the cathode pole piece adopting embodiment 1 ~ 6 gained blocky graphite negative material to prepare, expansion character, 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 testing result
As can be seen from Table 3, bounce-back, the expansion of the cathode pole piece adopting embodiment 1 ~ 6 gained blocky graphite negative material to prepare all are less than 23%.Experimental result shows, bounce-back, the expansion of cathode pole piece prepared by blocky graphite negative material of the present invention are less.
Claims (10)
1. a lithium ion battery blocky graphite negative material, is characterized in that: comprise blocky graphite matrix, described blocky graphite matrix surface is coated with graphite coat layer.
2. lithium ion battery blocky graphite negative material according to claim 1, is characterized in that: the D50 of this blocky graphite negative material is 12 ~ 20 μm, and tap density is 0.8 ~ 1.3g/cm
3, specific area is 1.1 ~ 2.4m
2/ g.
3. a preparation method for lithium ion battery blocky graphite negative material as claimed in claim 1, is characterized in that: comprise the following steps:
1) get after blocky graphite 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, after be down to room temperature, obtain carbonized material;
2) by step 1) gained carbonized material is incubated 5 ~ 7h and carries out graphitization processing under 2500 ~ 3000 DEG C of conditions, again through screening, except magnetic treatment, to obtain final product after being down to room temperature.
4. the preparation method of lithium ion battery blocky graphite negative material according to claim 3, is characterized in that: step 1) described in the mass ratio of blocky graphite matrix and covering be 1:0.03 ~ 0.06.
5. the preparation method of blocky graphite negative material of the lithium ion battery according to claim 3 or 4, is characterized in that: described covering is pitch, furane resins or ethylene-ethylacrylate resin.
6. the preparation method of blocky graphite negative material of the lithium ion battery according to claim 3 or 4, it is characterized in that: step 1) in, the purity of described blocky graphite matrix is 99.95% ~ 99.99%, D50 is 8.5 ~ 17.5 μm, and tap density is 0.8 ~ 1.0g/cm
3, specific area is 5.5 ~ 9.5m
2/ g.
7. the preparation method of lithium ion battery blocky graphite negative material according to claim 6, is characterized in that: described blocky graphite matrix is prepared by following methods:
Get blocky graphite particle, pulverize, after adopting alkali acid system to carry out chemical purification, after cleaning, drying, high temperature purification, after being down to room temperature, secondary shatters and obtains blocky graphite matrix again.
8. the preparation method of lithium ion battery blocky graphite negative material according to claim 7, it is characterized in that: described alkali acid system is that blocky graphite, NaOH solid and deionized water are melted 1 ~ 2h by mass ratio alkali at 500 ~ 600 DEG C of 1:0.2 ~ 0.4:0.6 ~ 0.8, washing and drying after again with hydrochloric acid constant temperature acidleach 2 ~ 3h under 70 ~ 90 DEG C of conditions that concentration is 13% ~ 17%, finally washing and drying.
9. the preparation method of lithium ion battery blocky graphite negative material according to claim 7, is characterized in that: described high temperature purification is incubated 0.5 ~ 1.5h under 2000 ~ 3000 DEG C of conditions.
10. a lithium ion battery, is characterized in that: adopt blocky graphite negative material according to claim 1 as negative material.
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Denomination of invention: The invention relates to a block graphite anode material for lithium ion battery, a preparation method and a lithium ion battery Effective date of registration: 20210220 Granted publication date: 20161109 Pledgee: Luoyang Rural Commercial Bank Co.,Ltd. Hanghe Branch Pledgor: LUOYANG YUEXING NEW ENERGY TECHNOLOGY Co.,Ltd. Registration number: Y2021980001239 |
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