CN105731427B - A kind of graphite negative material of lithium ion battery and preparation method thereof - Google Patents
A kind of graphite negative material of lithium ion battery and preparation method thereof Download PDFInfo
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- CN105731427B CN105731427B CN201410767840.0A CN201410767840A CN105731427B CN 105731427 B CN105731427 B CN 105731427B CN 201410767840 A CN201410767840 A CN 201410767840A CN 105731427 B CN105731427 B CN 105731427B
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Abstract
The invention discloses a kind of graphite negative material of lithium ion battery and preparation method thereof.The preparation method includes the following steps：1. the mixture of natural graphite and adhesive is carried out heating kneading；2. hip moulding；3. charing process；4. graphitization processing；5. crushing and classification, you can；The temperature of the hip moulding is 500~1000 DEG C, and pressure is 50~100MPa.Lithium ion battery negative material tap density produced by the present invention is high, and discharge capacity is big and good cycle, reduction graphite particle internal void reduce the cycle performance expanded so as to improve material.
Description
Technical field
The present invention relates to field of lithium ion battery more particularly to a kind of graphite negative material of lithium ion battery and its preparation sides
Method.
Background technology
In recent years, with the micromation of electronic device, the secondary cell of large capacity low bulk is had increasing need for.Especially make us
What is attracted attention is lithium ion battery, compared with ni-Cd or Ni-MH battery, has higher energy density using lithium ion battery.Although
It has been directed to raising battery capacity at present and has carried out extensive research, still, with the raising to battery performance requirements, has needed carrying
The expansion of battery core is further decreased while high battery capacity.
As cathode material of lithium ion battery, the granular material such as metal or graphite is had studied at present.With
The increase of battery capacity, it is accordingly required in particular to can be with higher tap density (such as 1.20g/cm3Or 1.20g/cm3More than) make
Negative material.
Natural graphite has very high capacitance (＞ 350mAh/g), and disadvantage is there are structural instability, when in order to obtain more
High electrode density and when improving squeeze pressure, graphite cathode particle is easy to parallelly be orientated with collector, on entire electrode
Consistent orientation is generated, the graphite of lithium is inserted into due to generating, so obtained electrode is easy to expand.Electrode expansion makes battery-active
Fillable amount of the substance in unit volume reduces, and leads to the problem of battery capacity reduction.
To solve the above-mentioned problems, the prior art usually carries out high jolt ramming using calcining with the mode that addition pitch is combined
The preparation of density graphite negative material.
Japan Patent JP2000-182617 mixes the high crystalline graphite such as flake natural graphite with pitch or resin,
Through crushing, charing, graphitization and compound is made, the deficiency of natural graphite can be improved, i.e. first charge-discharge efficiency is high, cycle
Excellent, capacity is big and coating is excellent.
Japan Patent JP2002-373656 will be in 250~400 DEG C with height-oriented powdered graphite and softening point
Between asphalt phase melting mixing, then crush, be classified, calcining, graphitization and compound is made, this negative material combines graphite
High power capacity and mesophase pitch excellent specific property, show high efficiency and bulk density.
When above-mentioned graphite cathode material when high-tap density uses the problem is that, due to graphite cathode material rupture
With expose the more surface areas reacted with electrolyte, accelerate to react with electrolyte, lead to the reduction of efficiency for charge-discharge, together
When bring the problem of safety difference；And high current (3C~5C) charge-discharge performance of these graphite cathode materials is bad, and 3C~
Capacity retention ratio is no more than 70% under 5C charge and discharge.
In addition, since high-tap density causes particle to be easily broken, the space for serving as lithium ion tunnel in the electrodes subtracts
It is few, lithium ion mobility is damaged, part throttle characteristics is caused to decline.
Therefore, in order to improve the discharge capacity of lithium ion battery, the capacity for increasing active material is not only needed, but also need
The tap density of negative material is improved, and inhibits expansion when battery charging, maintains efficiency for charge-discharge and part throttle characteristics.
Invention content
The technical problem to be solved in the present invention be in order to overcome in the prior art graphite negative material of lithium ion battery shake
Real density is low, graphite particle internal void is big, graphite cathode material cycle performance is bad, high current (3C~5C) charge-discharge performance
Bad defect provides a kind of lithium ion battery graphite cathode material and preparation method thereof.The preparation method of the present invention can be with
The tap density of graphite cathode material is improved, graphite particle internal void is reduced, reduces expansion so as to improve the cyclicity of material
Energy.
The present invention is to solve above-mentioned technical problem by the following technical programs：
The present invention provides a kind of preparation methods of graphite negative material of lithium ion battery comprising following step：1. will
The mixture of natural graphite and adhesive carries out heating kneading；2. hip moulding；3. charing process；4. graphitization processing；
5. crushing and classification, you can；The temperature of the hip moulding is 500~1000 DEG C, and pressure is 50~100MPa.
Step 1. in, the natural graphite can be various natural graphite starting materials commonly used in the art, preferably
Spherical natural graphite.The median D50 of the natural graphite is preferably 15~25 μm.
Step 1. in, the adhesive is preferably one in asphalt, coal tar pitch, phenolic resin and epoxy resin
Kind is a variety of.
The mass ratio of the binder and the natural graphite is preferably (1:9)~(5:5).
The temperature that the heating is mediated is preferably 100~180 DEG C.
Step 2. in, the time of the hip moulding is preferably 1~10 hour, is more preferably 1~3 hour.
Step 2. in after hip moulding is handled, natural graphite cycle expansion character can be improved and extend its recycling
Service life.
Step 3. in, the temperature of the charing process is preferably 1100~2000 DEG C, the charing process when
Between preferably 1~10 hour.
Step 4. in, the method and condition of the graphitization processing can be the processing of this field ordinary graphiteization method and
Condition, general using conventional graphitization finishing stove, the temperature of the graphitization processing is preferably 2800~3000 DEG C, institute
The time for the graphitization processing stated is preferably 24~48 hours.
Step 5. in, the crushing and classification is not particularly limited, and generally first carries out coarse crushing, then carry out Crushing of Ultrafine, compared with
It is to be crushed to goodly until the median D50 of product is 15~25 μm.The coarse crushing can use jaw crusher into
Row coarse crushing.Crushing of Ultrafine can use the ultra-fine machinery in the laboratories HHJ-10 that Weifang Zhengyuan Powder Engineering Equipment Co., Ltd. produces
Pulverizer crushing and classification, it is 5~100HZ that fine parameter, which is preferably classified machine host frequency, outer classification rotating speed for 1000~
1500 revs/min, it is ensured that grain diameter and specific morphology disclosure satisfy that the requirement of the present invention preferably technical solution.
The granule-morphology of the product of the present invention is re-compounded specific morphology：Composite particles are inside and outside to form uniform hole
Gap, to reduce the Volumetric expansion in long circulating charge and discharge process.
The present invention also provides one kind graphite negative material of lithium ion battery made from above-mentioned preparation method.
By the obtained negative material of preparation method of the present invention can efficiently solve current material there are the problem of, it is described
Graphite be it is a kind of through with can graphited adhesive mediate and the natural graphite negative electrode material of hip moulding processing.Its
Middle natural graphite and adhesive heating kneading, hip moulding, charing process, graphitizable high temperature processing and crushing and classification process
Simple process is easy, and raw material sources are extensive and of low cost.As a result of heating kneading, hip moulding and crushing and classification
The methods of, cause product tap density obtained high, discharge capacity is big and good cycle, performance parameter are as shown in the table.
On the basis of common knowledge of the art, above-mentioned each optimum condition can be combined arbitrarily to get each preferable reality of the present invention
Example.
The reagents and materials used in the present invention are commercially available.
The positive effect of the present invention is that：The graphite cathode material of the present invention, effectively improves processing performance, carries
High discharge capacity and cycle efficieny, efficiency for charge-discharge is high, the small amount of expansion of when charging, manufactured button cell it is comprehensive
Function admirable is closed, is mainly had the advantage that：1. tap density is higher, it is greater than or equal to 1.20g/cm3；2. chemical property is good,
Discharge capacity is in 360mAh/g or more；3. discharge platform and platform conservation rate are higher；4. high rate during charging-discharging is preferable, and 3C~
Capacity retention ratio is 80% or more under 5C charge and discharge；5. good cycle (500 cycles, capacity keep >=89%)；6. safety
Property preferably (130 DEG C/60 minutes, not quick-fried, do not rise)；7. preferable to electrolyte and other additive adaptability；8. product property is steady
It is fixed, almost without difference between batch.
Description of the drawings
Fig. 1 is the scanning electron microscope (SEM) photograph of the graphite cathode material of the embodiment of the present invention 1.
Fig. 2 is the cycle performance curve of the graphite cathode material of the embodiment of the present invention 6.
Specific implementation mode
It is further illustrated the present invention below by the mode of embodiment, but does not therefore limit the present invention to the reality
It applies among a range.In the following examples, the experimental methods for specific conditions are not specified, according to conventional methods and conditions, or according to quotient
Product specification selects.
Embodiment 1
Asphalt be crushed to 0.1mm hereinafter, be alternately added under stirring 20kg spherical natural graphites (D50 be 19.1 μm) and
It is mixed in 5kg asphalt powders to kneading pot, carries out kneading processing, the temperature of kneading is 100 DEG C, after kneading, in tablet press machine
In be pressed into sheet, crush, be put into hot isostatic press and be molded, using argon gas medium, heating pressurization, in 500 DEG C of roasting temperature
1 hour is kept the temperature under degree and 50MPa pressure, then Temperature fall.Under the protection of nitrogen, and at a temperature of 1300 DEG C at charing
Reaction product, is cooled to room temperature, then carry out graphitizable high temperature processing (2800 DEG C) 48 hours by reason 300 minutes later.And carry out
Crushing and classification, first coarse crushing, again Crushing of Ultrafine, it is 15.35Hz to adjust Crushing of Ultrafine classification machine host frequency, set it is outer be classified rotating speed as
1000 revs/min, negative electrode of lithium ion battery hot isostatic pressing graphite material is made.Half-cell capacity 362.5mAh/g, first charge discharge efficiency
92.8%, 45 DEG C of cycle expansions 7.5% in 400 weeks.
The granule-morphology of the product of the present embodiment is re-compounded specific morphology：Composite particles are inside and outside to form uniform hole
Gap, to reduce the Volumetric expansion in long circulating charge and discharge process, specific granule-morphology is see attached drawing 1.
Embodiment 2
Asphalt be crushed to 0.1mm hereinafter, be alternately added under stirring 20kg spherical natural graphites (D50 be 19.5 μm) and
It is mixed in 5kg asphalt powders to kneading pot, carries out kneading processing, the temperature of kneading is 120 DEG C, after kneading, in tablet press machine
In be pressed into sheet, crush, be put into hot isostatic press and be molded, using argon gas medium, heating pressurization, in 500 DEG C of roasting temperature
1 hour is kept the temperature under degree and 50MPa pressure, then Temperature fall.Under the protection of nitrogen, and at a temperature of 1100 DEG C at charing
Reaction product, is cooled to room temperature, then carry out graphitizable high temperature processing (3000 DEG C) 48 hours by reason 360 minutes later.And carry out
Crushing and classification, first coarse crushing, again Crushing of Ultrafine, it is 5.26Hz to adjust Crushing of Ultrafine classification machine host frequency, set it is outer be classified rotating speed as
1200 revs/min, negative electrode of lithium ion battery hot isostatic pressing graphite material is made.Half-cell capacity 363.1mAh/g, first charge discharge efficiency
93.2%, 45 DEG C of cycle expansions 8.0% in 400 weeks.Granule-morphology is the same as embodiment 1.
Embodiment 3
Modified coal asphalt is crushed to 0.1mm, and hereinafter, being alternately added 12.5kg spherical natural graphites under stirring, (D50 is 20.1 μ
M) it and being mixed in 12.5kg asphalt powders to kneading pot, carries out kneading processing, the temperature of kneading is 160 DEG C, after kneading,
It is pressed into sheet in tablet press machine, crushes, is put into hot isostatic press and is molded, using argon gas medium, heating pressurization, in 500 DEG C
1 hour is kept the temperature under calcination temperature and 60MPa pressure, then Temperature fall.Under the protection of nitrogen, and at a temperature of 1500 DEG C
Reaction product, is cooled to room temperature by charing process 180 minutes later, then carries out graphitizable high temperature processing (3000 DEG C) 24 hours.
And crushing and classification is carried out, first coarse crushing, again Crushing of Ultrafine, it is 54Hz to adjust Crushing of Ultrafine classification machine host frequency, sets outer classification and turns
Speed is 1300 revs/min, and negative electrode of lithium ion battery hot isostatic pressing graphite material is made.Half-cell capacity 365.0mAh/g, is imitated for the first time
Rate 92.6%, 45 DEG C of cycle expansions 6.7% in 400 weeks.Granule-morphology is the same as embodiment 1.
Embodiment 4
Modified coal asphalt is crushed to 0.1mm, and hereinafter, being alternately added 17.5kg spherical natural graphites under stirring, (D50 is 15.2 μ
M) it and being mixed in 7.5kg asphalt powders to kneading pot, carries out kneading processing, the temperature of kneading is 180 DEG C, after kneading,
It is pressed into sheet in tablet press machine, crushes, is put into hot isostatic press and is molded, using argon gas medium, heating pressurization, in 800 DEG C
3 hours are kept the temperature under calcination temperature and 80MPa pressure, then Temperature fall.Under the protection of nitrogen, and at a temperature of 1600 DEG C
Reaction product, is cooled to room temperature by charing process 60 minutes later, then carries out graphitizable high temperature processing (2900 DEG C) 36 hours.And
Classification is crushed, first coarse crushing, again Crushing of Ultrafine, it is 100Hz to adjust Crushing of Ultrafine classification machine host frequency, and setting is outer to be classified rotating speed
It is 1500 revs/min, negative electrode of lithium ion battery hot isostatic pressing graphite material is made.Half-cell capacity 366.7mAh/g, first charge discharge efficiency
93.0%, 45 DEG C of cycle expansions 8.4% in 400 weeks.Granule-morphology is the same as embodiment 1.
Embodiment 5
Asphalt is crushed to 0.1mm hereinafter, being alternately added 17.5kg spherical natural graphites under stirring (D50 is 24.1 μm)
It is mixed in 7.5kg asphalt powders to kneading pot, carries out kneading processing, the temperature of kneading is 170 DEG C, after kneading, is being pressed
It is pressed into sheet in piece machine, crushes, is put into hot isostatic press and is molded, using argon gas medium, heating pressurization, in 800 DEG C of roastings
It burns and keeps the temperature 3 hours under temperature and 80MPa pressure, then Temperature fall.Under the protection of nitrogen, and charcoal at a temperature of 1100 DEG C
Change processing 600 minutes, is later cooled to room temperature reaction product, then carry out graphitizable high temperature processing (3000 DEG C) 48 hours.And
Classification is crushed, first coarse crushing, again Crushing of Ultrafine, it is 47.22Hz to adjust Crushing of Ultrafine classification machine host frequency, sets outer classification and turns
Speed is 1000 revs/min, and negative electrode of lithium ion battery hot isostatic pressing graphite material is made.Half-cell capacity 362.4mAh/g, is imitated for the first time
Rate 92.8%, 45 DEG C of cycle expansions 7.3% in 400 weeks.Granule-morphology is the same as embodiment 1.
Embodiment 6
Asphalt is crushed to 0.1mm hereinafter, being alternately added 22.5kg spherical natural graphites under stirring (D50 is 18.5 μm)
It is mixed in 2.5kg asphalt powders to kneading pot, carries out kneading processing, the temperature of kneading is 160 DEG C, after kneading, is being pressed
It is pressed into sheet in piece machine, crushes, is put into hot isostatic press and is molded, using argon gas medium, heating pressurization, in 800 DEG C of roastings
It burns and keeps the temperature 3 hours under temperature and 80MPa pressure, then Temperature fall.Under the protection of nitrogen, and charcoal at a temperature of 1100 DEG C
Change processing 300 minutes, is later cooled to room temperature reaction product, then carry out graphitizable high temperature processing (3000 DEG C) 48 hours.And
Classification is crushed, first coarse crushing, again Crushing of Ultrafine, it is 15.67Hz to adjust Crushing of Ultrafine classification machine host frequency, sets outer classification and turns
Speed is 1100 revs/min, and negative electrode of lithium ion battery hot isostatic pressing graphite material is made.Half-cell capacity 366.1mAh/g, is imitated for the first time
Rate 92.4%, 45 DEG C of cycle expansions 5.4% in 400 weeks.Granule-morphology is the same as embodiment 1.
Embodiment 7
17.5kg spherical natural graphites (D50 be 19.1 μm) and 7.5kg epoxy powders are alternately added under stirring to pinching
It closes and is mixed in pot, carry out kneading processing, the temperature of kneading is 140 DEG C, and after kneading, sheet is pressed into tablet press machine, is crushed,
It is put into hot isostatic press and is molded, using argon gas medium, heating pressurization, under 1000 DEG C of calcination temperatures and 100MPa pressure
10 hours are kept the temperature, then Temperature fall.Under the protection of nitrogen, and charing process 300 minutes at a temperature of 1100 DEG C, later
Reaction product is cooled to room temperature, then carries out graphitizable high temperature processing (2800 DEG C) 30 hours.And crushing and classification is carried out, first coarse powder
Broken, Crushing of Ultrafine again, it is 49.38Hz to adjust Crushing of Ultrafine classification machine host frequency, set outer classification rotating speed as 1000 revs/min, obtained
Negative electrode of lithium ion battery hot isostatic pressing graphite material.Half-cell capacity 363.6mAh/g, first charge discharge efficiency 92.6%, 45 DEG C 400 weeks
Cycle expansion 6.9%.Granule-morphology is the same as embodiment 1.
Embodiment 8
20kg spherical natural graphites (D50 is 19.5 μm) and 5kg Phenolic resin powders (the limited public affairs of Wuxi City A Erzi chemical industry
Department) it is alternately added in kneading pot and mixes under stirring, kneading processing is carried out, the temperature of kneading is 160 DEG C, after kneading,
It is pressed into sheet in tablet press machine, crushes, is put into hot isostatic press and is molded, using argon gas medium, heating pressurization, in 1000 DEG C
10 hours are kept the temperature under calcination temperature and 100MPa pressure, then Temperature fall.Under the protection of nitrogen, and in 1100 DEG C of temperature
Reaction product, is cooled to room temperature by lower charing process 300 minutes later, then to carry out graphitizable high temperature processing (2800 DEG C) 24 small
When.And crushing and classification is carried out, first coarse crushing, again Crushing of Ultrafine, it is 9.22Hz, outer point of setting to adjust Crushing of Ultrafine classification machine host frequency
Grade rotating speed is 1000 revs/min, and negative electrode of lithium ion battery hot isostatic pressing graphite material is made.Half-cell capacity 362.7mAh/g, it is first
Secondary efficiency 92.3%, 45 DEG C of cycle expansions 7.1% in 400 weeks.Granule-morphology is the same as embodiment 1.
Comparative example 1
Asphalt is crushed to 0.1mm hereinafter, being alternately added 17.5kg spherical natural graphites under stirring (D50 is 19.5 μm)
It is mixed in 7.5kg asphalt powders to kneading pot, carries out kneading processing, the temperature of kneading is 150 DEG C, after kneading, is being pressed
It is pressed into sheet in piece machine, crushes compound stalk forming.Under the protection of nitrogen, and charing process 120 minutes at a temperature of 1100 DEG C,
Reaction product is cooled to room temperature later.And crushing and classification is carried out, first coarse crushing, again Crushing of Ultrafine adjust Crushing of Ultrafine and are classified owner
Unit frequency is 16.41Hz, sets outer classification rotating speed as 1000 revs/min, graphite material at negative is made, half-cell holds
Measure 345.2mAh/g, first charge discharge efficiency 87.6%, 45 DEG C of cycle expansions 15.3% in 400 weeks.
Comparative example 2
Modified coal asphalt is crushed to 0.1mm, and hereinafter, being alternately added 17.5 kilograms of spherical natural graphites under stirring, (D50 is
15.2 μm) and 7.5 kilograms of asphalt powders to kneading pot in mix, carry out kneading processing, the temperature of kneading is 120 DEG C, mediates knot
Shu Hou is pressed into sheet in tablet press machine, crushes, is put into cold isostatic press and is molded.Under the protection of nitrogen, and at 1600 DEG C
At a temperature of charing process 60 minutes, reaction product is cooled to room temperature later.Graphitizable high temperature processing (3000 DEG C) 48 is carried out again
Hour.And crushing and classification is carried out, first coarse crushing, again Crushing of Ultrafine, it is 15.64Hz, setting to adjust Crushing of Ultrafine classification machine host frequency
Outer classification rotating speed is 1000 revs/min, and negative electrode of lithium ion battery cold isostatic pressing formed graphite material is made.Half-cell capacity 354.5mAh/
G, first charge discharge efficiency 89.1%, 400 weeks cycles at 45 DEG C are expanded to 12.0%.
Comparative example 3
Modified coal asphalt is crushed to 0.1mm, and hereinafter, being alternately added 12.5kg spherical natural graphites under stirring, (D50 is 20.1 μ
M) it and being mixed in 12.5kg asphalt powders to kneading pot, carries out kneading processing, the temperature of kneading is 160 DEG C, after kneading,
It is pressed into sheet in tablet press machine, crushes, is put into hot isostatic press and is molded, using argon gas medium, heating pressurization, in 400 DEG C
5 hours are kept the temperature under calcination temperature and 30MPa pressure, then Temperature fall.Under the protection of nitrogen, and at a temperature of 1500 DEG C
Reaction product, is cooled to room temperature by charing process 180 minutes later, then carries out graphitizable high temperature processing (3000 DEG C) 24 hours.
And crushing and classification is carried out, first coarse crushing, again Crushing of Ultrafine, it is 54Hz to adjust Crushing of Ultrafine classification machine host frequency, sets outer classification and turns
Speed is 1300 revs/min, and negative electrode of lithium ion battery hot isostatic pressing graphite material is made.Half-cell capacity 354.8mAh/g, is imitated for the first time
Rate 91.5%, 45 DEG C of cycle expansions 11.4% in 400 weeks.
Half-cell test method used in the present invention is：Graphite sample, the N- methylpyrroles containing 6~7% Kynoar
Alkanone and 2% conductive black be uniformly mixed, be applied on copper foil, by the pole piece coated be put into temperature be 110 DEG C of vacuum drying chambers
It is middle vacuum drying 4 hours it is spare.Simulated battery is assemblied in the German Braun glove box of applying argon gas and carries out, electrolyte 1M
LiPF6+EC: DEC: DMC=1: 1: 1 (volume ratio), metal lithium sheet are to electrode, and electrochemical property test is in the U.S.
It is carried out on ArbinBT2000 type cell testers, charging/discharging voltage ranging from 0.005 to 1.0V, charge-discharge velocity 0.1C.
Full battery test method used in the present invention is：The graphite of the embodiment of the present invention or comparative example makees cathode, and cobalt acid lithium is made
Anode, 1M-LiPF6EC: DMC: EMC=1: 1: 1 (volume ratio) solution are assembled into full battery, test 1C charge and discharges 500 as electrolyte
All capacity retention ratios are 89.4%, as shown in Fig. 2, test sample is 6 gained sample of embodiment.
The performance parameter of each embodiment and comparative example is as shown in the table：
From data above as can be seen that the product tap density of comparative example 1 is low, discharging efficiency is low for the first time, is 87.6%,
Discharge capacity is only 345.2mAh/g, and recycles expansion greatly, and capacity retention ratio is low under 3C~5C charge and discharge；Comparative example 2 is cold etc. quiet
Suppress negative material tap density it is low, discharge capacity is low, is 354.5mAh/g, and it is big to recycle expansion, 3C~5C charge and discharge
Lower capacity retention ratio is low；The tap density of comparative example 3 is low, and discharge capacity and efficiency are low for the first time, and recycles expansion greatly, and 3C~
Capacity retention ratio is low under 5C charge and discharge；Negative material prepared by preparation method using the present invention, tap density can control
More than or equal to 1.20g/cm3, discharge capacity up to 360mAh/g or more, under 3C~5C charge and discharge capacity retention ratio 80% with
On.
The product gram volume and tap density of the present invention is higher, reduces the loss of irreversible capacity, it is close to improve energy
Degree reduces the dosage of anode；Specific surface area is controlled in suitable range, both can guarantee that particle surface pore was flourishing, porosity can
Reach 5~6%, and be conducive to that lithium-ion battery system is inhibited to generate ballooning, battery has a safety feature (130 DEG C/60 points
Clock, it is not quick-fried, do not rise)；Over-charging is preferable；Good cycle, capacity retention ratio can reach 89.4% after recycling 500 times, for
Natural graphite negative electrode material significantly improves effect in high-tap density using the shortcomings that poor circulation, as shown in Figure 2.To electricity
It solves liquid and other additive adaptability is preferable, 0 DEG C of 10 weeks cycle is without analysis lithium, and high current (3C~5C) charge-discharge performance is good, capacity
Conservation rate is 80% or more.And existing product high current (3C~5C) charge and discharge inferior pole piece analyses lithium, capacity retention ratio is 50%
Left and right, is only capable of using under 2C charge and discharge.
Claims (4)
1. a kind of preparation method of graphite negative material of lithium ion battery comprising following step：1. by natural graphite and bonding
The mixture of agent carries out heating kneading；2. hip moulding；3. charing process；4. graphitization processing；5. crushing and classification, i.e.,
It can；The adhesive is one or more in asphalt, coal tar pitch, phenolic resin and epoxy resin；The bonding
The mass ratio of agent and the natural graphite is (1:9)~(5:5)；The temperature that the heating is mediated is 100~180 DEG C；Institute
The crushing and classification stated is first to carry out coarse crushing, then carry out Crushing of Ultrafine, and the fine parameter is：Being classified machine host frequency is
5~100HZ, outer classification rotating speed are 1000~1500 revs/min；The temperature of the hip moulding is 500~1000 DEG C, institute
The pressure for the hip moulding stated is 50~100MPa, and the time of the hip moulding is 1~10 hour；Described
The temperature of charing process is 1100~2000 DEG C, and the time of the charing process is 1~10 hour；The graphitization processing
Temperature be 2800~3000 DEG C, time of the graphitization processing is 24~48 hours.
2. preparation method as described in claim 1, which is characterized in that the median D50 of the natural graphite be 15~
25μm。
3. preparation method as described in claim 1, which is characterized in that the crushing and classification is the middle position grain for being crushed to product
Until diameter D50 is 15~25 μm.
4. a kind of graphite negative material of lithium ion battery made from preparation method according to any one of claims 1 to 3.
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| CN107871866A (en) * | 2016-09-27 | 2018-04-03 | 宁波杉杉新材料科技有限公司 | A kind of preparation method of high magnification natural graphite negative electrode material |
| CN108630940B (en) * | 2017-03-24 | 2021-07-13 | 宁波杉杉新材料科技有限公司 | Preparation method of high-capacity natural graphite negative electrode material |
| CN107814382B (en) * | 2017-09-28 | 2019-12-10 | 广东东岛新能源股份有限公司 | Long-life modified natural graphite negative electrode material and preparation method and application thereof |
| CN113903916A (en) * | 2017-11-06 | 2022-01-07 | 上高县荣炭科技有限公司 | Application of coupling agent in granulation process of lithium battery negative electrode material and granulation process of lithium battery negative electrode material |
| US11923543B2 (en) * | 2018-04-27 | 2024-03-05 | Panasonic Intellectual Property Management Co., Ltd. | Nonaqueous electrolyte secondary battery |
| CN111244450A (en) * | 2018-11-29 | 2020-06-05 | 贝特瑞新材料集团股份有限公司 | Natural graphite, modified natural graphite material prepared from natural graphite, preparation method and application |
| CN111320171B (en) * | 2018-12-17 | 2023-08-01 | 贝特瑞新材料集团股份有限公司 | Low-expansion graphite negative electrode material, preparation method thereof and lithium ion battery |
| CN111215633A (en) * | 2020-01-14 | 2020-06-02 | 大同新成新材料股份有限公司 | Method for preparing lithium ion negative electrode material by using tin graphene composite material |
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| CN112366315A (en) * | 2020-11-30 | 2021-02-12 | 河南开炭新材料设计研究院有限公司 | Production method of lithium battery negative electrode material |
| CN112479200A (en) * | 2020-12-24 | 2021-03-12 | 河南开炭新材料设计研究院有限公司 | Method for producing cathode material by using waste heat with co-firing |
| CN113023724A (en) * | 2021-02-26 | 2021-06-25 | 四川东岛新能源有限公司 | Preparation method of high-rate graphite negative electrode material for lithium ion power battery |
| CN113831128B (en) * | 2021-09-30 | 2023-02-28 | 宁波江丰电子材料股份有限公司 | Processing method for graphite hot isostatic pressing |
| CN115196630A (en) * | 2022-06-07 | 2022-10-18 | 谢艳 | Preparation method for improving tap density of carbon electrode material for energy storage device |
| CN116741989A (en) * | 2022-09-30 | 2023-09-12 | 云南锂宸新材料科技有限公司 | Preparation method of natural graphite anode material, product thereof and application of natural graphite anode material in lithium ion battery |
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| JP2000182617A (en) * | 1998-12-16 | 2000-06-30 | Nkk Corp | Carbon material for lithium secondary battery electrode and its manufacture, and lithium secondary battery |
| CN100503434C (en) * | 2006-03-07 | 2009-06-24 | 宁波杉杉新材料科技有限公司 | Method of preparing isotropic carbon material and prepared carbon material |
| CN104037417B (en) * | 2013-03-04 | 2017-12-01 | 上海杉杉科技有限公司 | A kind of modified natural graphite and preparation method thereof |
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