CN105336917A - Lithium ion battery and its negative electrode sheet preparation method - Google Patents
Lithium ion battery and its negative electrode sheet preparation method Download PDFInfo
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Abstract
The invention discloses a lithium ion battery and its negative electrode sheet preparation method. The method comprises the following steps: 1) coating the surface of a first negative active material with obvious volume effect with a foaming agent to prepare a first negative active material coated by the foaming agent; 2) adding the first negative active material coated by the foaming agent, a carbon material, a binder and a conductive agent in proportion in a first solvent which cannot dissolve the foaming agent, fully stirring the materials to obtain a cathode slurry; and 3) uniformly coating the cathode slurry prepared in the step 2) on a negative current collector, and removing the foaming agent through heat treatment to obtain the negative electrode sheet. In addition, the invention also discloses a lithium ion battery. The preparation method of the negative electrode sheet of the lithium ion battery can effectively reduce expansion of the first negative active material with obvious volume effect in the negative electrode of the lithium ion battery during charge and discharge processes, can improve the cycle performance of the lithium ion battery, and can increase the energy density of the lithium ion battery.
Description
Technical field
The invention belongs to technical field of lithium ion, more particularly, the present invention relates to the preparation method of a kind of lithium ion battery and negative plate thereof, its can reduce in negative pole containing bulk effect significantly can embedding lithium active material lithium ion battery circulation expand.
Background technology
In recent years, along with smart mobile phone, panel computer, wearable device universal, also more and more higher to the requirement of the energy density of consumption Li-like ions battery.
Silica-based, tin-based material due to capacity large and de-/intercalation potential is low, is the ideal material of lithium ion battery with high energy density negative electrode active material of future generation.But, serious volumetric expansion and contraction is there is in this type of material in de-/embedding lithium process, the destruction of material structure, the fragmentation of active material particle can be caused and come off from collector, cause lithium ion battery to be out of shape, expand and the sharply deterioration of chemical property, be therefore difficult to commercially obtain application.
In order to overcome above-mentioned defect, a kind of effective method is that this type of capacity is large but the obvious material of bulk effect prepares negative plate as negative electrode active material after mixing with material with carbon element.With simple material with carbon element as compared with negative electrode active material, above-mentioned mixing negative electrode active material can not only keep good cycle performance, also effectively can improve discharge capacity, promotes energy density.But, when preparing negative plate, the change in volume of different types of negative active core-shell material in embedding/de-lithium process is inconsistent, such as, the change in volume of silicon, tin-based active material will be far longer than the change in volume of material with carbon element, cause the internal structure of negative plate unstable, therefore still effectively can not suppress the dilatancy after the long-term charge and discharge cycles of lithium ion battery.
In view of this, necessaryly provide a kind of and effectively can suppress the lithium ion battery of lithium ion battery dilatancy and the preparation method of negative plate thereof.
Summary of the invention
The object of the invention is to: overcome the deficiencies in the prior art, provide a kind of and effectively can suppress the lithium ion battery of lithium ion battery dilatancy and the preparation method of negative plate thereof.
In order to realize foregoing invention object, the invention provides a kind of preparation method of anode plate for lithium ionic cell, it comprises the following steps:
1) blowing agent is coated on the obvious first negative electrode active material surface of bulk effect, obtained the first negative electrode active material being coated with blowing agent;
2) by step 1) in obtained the first negative electrode active material being coated with blowing agent, material with carbon element, binding agent, conductive agent add in proportion and do not dissolve in the first solvent of blowing agent, obtain cathode size after fully stirring; And
3) by step 2) in obtained cathode size be spread evenly across on negative current collector, drying, leave standstill, cold pressing, obtain negative plate after heat treatment removing blowing agent.
One as the preparation method of anode plate for lithium ionic cell of the present invention is improved, and described first negative electrode active material is one or more in silicon (Si), tin (Sn), germanium (Ge), the simple substance of antimony (Sb), alloy or compound.
One as the preparation method of anode plate for lithium ionic cell of the present invention is improved, described blowing agent be selected from Celogen Az, azodiisobutyronitrile, N, N-dinitrosopentamethylene tetramine, benzene sulfonyl hydrazide, p-toluene sulfonylsemicarbazide one or more.
One as the preparation method of anode plate for lithium ionic cell of the present invention is improved, and described blowing agent volume is the 80%-120% of the first negative electrode active material volume.
One as the preparation method of anode plate for lithium ionic cell of the present invention is improved, and described first solvent is water.
One as the preparation method of anode plate for lithium ionic cell of the present invention is improved, and described heat treated temperature is 80-250 DEG C.Heat treated temperature needs the decomposition temperature higher than blowing agent, just can make to occur space around the first active material, for the first active material provides expansion space.
One as the preparation method of anode plate for lithium ionic cell of the present invention is improved, and described method blowing agent being coated on the first negative polarity material surface comprises:
1) blowing agent and the first negative electrode active material are added in ball grinder;
2) control ratio of grinding media to material, ball milling speed, ball milling interval leave standstill heat radiation time and Ball-milling Time, the first negative electrode active material that after ball milling, obtained blowing agent is coated.
One as the preparation method of anode plate for lithium ionic cell of the present invention is improved, and described ratio of grinding media to material is 3:1-5:1.
One as the preparation method of anode plate for lithium ionic cell of the present invention is improved, and described ball milling speed is 500-800r/min.
One as the preparation method of anode plate for lithium ionic cell of the present invention is improved, and described ball milling interval leaves standstill the heat radiation time for the 30min that dispelled the heat every 2 hours.
One as the preparation method of anode plate for lithium ionic cell of the present invention is improved, and described Ball-milling Time is 8-12h.
If ball milling speed is too high, overlong time will increase the specific area of active material greatly, causes battery side reaction aggravation in charge and discharge process, worsens cycle performance; If ball milling speed is too small, the time is too short, then blowing agent is failed to realize coated or not exclusively coated.
One as the preparation method of anode plate for lithium ionic cell of the present invention is improved, and described method blowing agent being coated on the first negative electrode active material surface comprises:
1) be dissolved in the second solvent by blowing agent and obtain solution, wherein, the boiling point of the second solvent, lower than the decomposition temperature of blowing agent, decomposes to avoid blowing agent in spray-drying process;
2) appropriate first negative electrode active material is added step 1) in preparation solution in stir acquisition suspension-turbid liquid; And
3) by step 2) in obtained suspension-turbid liquid atomization drying in spray dryer, the first negative electrode active material that obtained blowing agent is coated.
One as the preparation method of anode plate for lithium ionic cell of the present invention is improved, and the boiling point of described second solvent is lower than the decomposition temperature more than 20 DEG C of blowing agent.
One as the preparation method of anode plate for lithium ionic cell of the present invention is improved, and described method blowing agent being coated on the first negative electrode active material surface comprises:
1) blowing agent is dissolved in the second solvent obtains solution;
2) the first negative electrode active material is joined step 1) in obtained solution and the acquisition suspension-turbid liquid that stirs;
3) to step 2) in add in obtained suspension-turbid liquid do not dissolve blowing agent but with step 1) in the first solvent of dissolving each other of the second solvent, in adition process, blowing agent is separated out gradually from solution, and is coated on the first negative electrode active material surface; And
4) by step 3) in obtained suspension-turbid liquid filter, wash, obtain the first coated negative electrode active material of blowing agent after dry, grinding.
One as the preparation method of anode plate for lithium ionic cell of the present invention is improved, described second solvent be selected from methyl-sulfoxide, methyl alcohol, ethanol, ether, acetone one or more.
In addition, present invention also offers a kind of lithium ion battery, it comprises positive plate, negative plate, is interval in barrier film between positive plate and negative plate, and electrolyte, wherein, negative plate is the negative plate obtained according to the preparation method of aforementioned anode plate for lithium ionic cell.
Relative to prior art, the preparation method of lithium ion battery of the present invention and negative plate thereof has the following advantages:
1. blowing agent is coated on the obvious first anode active material particles surface of volumetric expansion, through heat treatment, blowing agent decomposes, can be that the expansion of the first anode active material particles reserves enough spaces, extruding between the adjacent cathode active material particle that the expansion because of the first negative electrode active material can be avoided to cause, also the excessive bounce-back of cathode membrane can not be caused to expand, thus reduce expansion and the distortion of lithium ion battery, be conducive to keeping the unimpeded of whole electrodes conduct network, therefore the cycle performance of lithium ion battery can be improved, maintain the high-energy-density in circulating battery process.
2. optionally blowing agent is coated on the first anode active material particles surface that volumetric expansion is more obvious, discharge capacity is higher, then it is mixed with material with carbon element, the discharge capacity of lithium ion battery can be improved, the energy density reduction that the equal encapsulated blowing agent of all negative electrode active materials causes can be avoided again.
Embodiment
In order to make goal of the invention of the present invention, technical scheme and technique effect more clear, below in conjunction with embodiment and comparative example, the present invention is described in more detail.Should be understood that, the embodiment described in this specification is just in order to explain the present invention, and be not intended to limit the present invention, the formula, ratio etc. of embodiment can suit measures to local conditions make a choice and there is no substantial effect to result.
It should be noted that, the present invention includes first at the preprocessing process of the obvious first negative electrode active material Surface coating blowing agent of bulk effect, the blowing agent used needs not by the first dissolution with solvents in cathode size whipping process, namely solubility is lower than 0.01g/100ml, to reach the object that coated blowing agent is the obvious first negative electrode active material expansion headspace of bulk effect after the heat treatment.
In addition, the coated blowing agent volume of the present invention is the 80%-120% of the first negative electrode active material volume, when coated foaming dosage very little time, reserve sufficient space cannot to the expansion of the first negative electrode active material, easily cause the instability of negative pole structure, cause larger cell expansion and distortion.When coated foaming agents content is too much, the waste in negative pole space and the reduction of battery energy density beyond the space shared by the first negative electrode active material expansion, are caused in reserved space.
Embodiment 1
1. prepare the first negative electrode active material that blowing agent is coated
1) be dissolved in methyl-sulfoxide by Celogen Az, preparation mass percentage is the Celogen Az solution of 3.5%;
2) appropriate SiO powder is added step 1) in stir in obtained solution acquisition suspension-turbid liquid, wherein, the volume of Celogen Az is 100% of SiO volume;
3) by step 2) in obtained suspension-turbid liquid at 190 DEG C, carry out spraying dry after the coated SiO of obtained Celogen Az.
2. prepare anode plate for lithium ionic cell
1) SiO coated to Delanium, Celogen Az, polyacrylic acid (PAA), sodium carboxymethylcellulose (CMC), conductive carbon (SP) are added in appropriate amount of deionized water, the mass ratio of Delanium: SiO (not comprising blowing agent quality): PAA:CMC:SP is 81:9:7:1:2, stir at 30 DEG C, obtain the cathode size that solid content is 42%;
2) by step 1) in obtained cathode size be spread evenly across on negative current collector Copper Foil, through 100 DEG C of dry 30min, 30 tons of pressure are colded pressing, and at 200 DEG C, vacuum heat 2h removes Celogen Az, obtains negative plate.
3. prepare based lithium-ion battery positive plate
By positive active material LiCoO
2, conductive carbon SP, binding agent Kynoar (PVDF) in mass ratio 95:2:3 mix in solvent N-methyl pyrilidone (NMP) and make the anode sizing agent that solid content is 70%, anode sizing agent is evenly coated on plus plate current-collecting body aluminium foil, dry 30min at 110 DEG C, colds pressing and rear obtained positive plate of cutting into slices.
4. prepare lithium-ion battery electrolytes
By ethylene carbonate (EC), propene carbonate (PC), methyl ethyl carbonate (DEC), fluorinated ethylene carbonate (FEC) in mass ratio 25:25:45:5 fully mix, add solute lithium hexafluoro phosphate (LiPF
6), LiPF
6concentration is 1.1mol/L, obtained lithium-ion battery electrolytes.
5. prepare lithium ion battery
Through winding and encapsulation, the based lithium-ion battery positive plate prepared above, negative plate, polyethylene (PE) barrier film are made that thickness is about 4mm, width is 35mm, length is the lithium ion battery of 80mm, at 75 DEG C, after vacuum bakeout 12h, inject electrolyte and leave standstill 24h; Then, at 35 DEG C, use the constant current charge of 0.1C to 4.35V, then 0.05C is dropped to 4.35V constant-potential charge to electric current, 3.0V is discharged to the constant current of 0.5C, repeat 2 discharge and recharges, last with the constant current of 0.5C by lithium ion cell charging to 3.85V, complete the preparation of lithium ion battery.
Embodiment 2
1. prepare the first negative electrode active material that blowing agent is coated
1) be dissolved in methyl-sulfoxide by Celogen Az, preparation mass percentage is the Celogen Az solution of 2.5%;
2) appropriate SiO powder is added step 1) in stir in obtained solution, make the volume of Celogen Az be 100% of SiO volume;
3) to step 2) in slowly drip water in obtained suspension-turbid liquid and constantly stir, until amount of water is equal with methyl-sulfoxide quality, in adition process, blowing agent is separated out gradually from solution, is coated on SiO surface;
4) by step 3) in obtained suspension-turbid liquid filter, wash, namely obtain the coated SiO of Celogen Az after dry, grinding.
2. prepare based lithium-ion battery positive plate
Positive active material adopts ternary material LiNi
(1/3)co
(1/3)mn
(1/3)o
2by itself and conductive carbon (SP), Kynoar (PVDF) in mass ratio 94:2:4 stir in solvent N-methyl pyrilidone (NMP), make the anode sizing agent that solid content is 70%, anode sizing agent is coated in equably on plus plate current-collecting body aluminium foil, dry 30min at 110 DEG C, colds pressing and rear obtained positive plate of cutting into slices.
Prepare anode plate for lithium ionic cell, prepare lithium-ion battery electrolytes, and prepare lithium ion battery with embodiment 1.
Embodiment 3
1. prepare the first negative electrode active material that blowing agent is coated
1) by blowing agent azodiisobutyronitrile and Sn
51si
30c
19alloy powder by volume 1:1 adds in ball grinder;
2) ball-milling material is zirconia, and ratio of grinding media to material is 5:1, and rotational speed of ball-mill is 600r/min, and every ball milling 2h stops ball milling 30min, Ball-milling Time 10h, the Sn that after ball milling, obtained azodiisobutyronitrile is coated
51si
30c
19alloy material.
2. prepare anode plate for lithium ionic cell
1) by Sn coated to Delanium, azodiisobutyronitrile
51si
30c
19alloy, butadiene-styrene rubber (SBR), sodium carboxymethylcellulose (CMC), conductive carbon (SP) mix, Delanium: Sn
51si
30c
19alloy (disregarding blowing agent quality): the mass ratio of SBR:CMC:SP is 81:9:6:2:2, stirs after adding suitable quantity of water at 30 DEG C, obtains the cathode size that solid content is 45%;
2) by step 1) in obtained cathode size be spread evenly across on negative current collector Copper Foil, through 60 DEG C of dry 20min, 30 tons of pressure are colded pressing, and at 80 DEG C, vacuum heat 2h obtains negative plate after removing azodiisobutyronitrile.
Prepare based lithium-ion battery positive plate, prepare lithium-ion battery electrolytes, prepare lithium ion battery with embodiment 1.
Embodiment 4
Prepare lithium ion battery according to the method for embodiment 1, difference is only: when preparing coated the first negative electrode active material of blowing agent, the volume of Celogen Az is 120% of SiO volume.
Embodiment 5
Prepare lithium ion battery according to the method for embodiment 1, difference is only: when preparing coated the first negative electrode active material of blowing agent, the volume of Celogen Az is 110% of SiO volume.
Embodiment 6
Prepare lithium ion battery according to the method for embodiment 1, difference is only: when preparing coated the first negative electrode active material of blowing agent, the volume of Celogen Az is 90% of SiO volume.
Embodiment 7
Prepare lithium ion battery according to the method for embodiment 1, difference is only: when preparing coated the first negative electrode active material of blowing agent, the volume of Celogen Az is 80% of SiO volume.
Comparative example 1
Prepare lithium ion battery according to the method for embodiment 1, difference is only: eliminate step 1) at the first negative electrode active material Surface coating blowing agent, i.e. the not coated Celogen Az in SiO surface.
Comparative example 2
Prepare lithium ion battery according to the method for embodiment 2, difference is only: eliminate step 1) at the first negative electrode active material Surface coating blowing agent, i.e. the not coated Celogen Az in SiO surface.
Comparative example 3
Prepare lithium ion battery according to the method for embodiment 3, difference is only: eliminate step 1) at the first negative electrode active material Surface coating blowing agent, i.e. Sn
51si
30c
19the not coated azodiisobutyronitrile of alloy surface.
Comparative example 4
Prepare lithium ion battery according to the method for embodiment 1, difference is only: when preparing coated the first negative electrode active material of blowing agent, the volume of Celogen Az is 130% of SiO volume.
Comparative example 5
Prepare lithium ion battery according to the method for embodiment 1, difference is only: when preparing coated the first negative electrode active material of blowing agent, the volume of Celogen Az is 70% of SiO volume.
Performance of lithium ion battery is tested
1. lithium ion battery energy density test
At 25 DEG C, with 0.5C constant current by lithium ion cell charging to 4.35V, then with the constant-potential charge of 4.35V to electric current for 0.05C, test lithium ion battery volume (L); Then, with the constant current of 0.5C, lithium ion battery is discharged to 3.0V, testing the discharge energy obtained is initial discharge energy (Wh), and the energy density calculated is first energy density.According to upper type, test discharge energy (Wh) and the volume (L) of lithium ion battery the 50th time, 100 times, 200 times circulations, calculate the energy density (Wh/L) of the 50th time, 100 times, 200 times circulations.
The energy density of lithium ion battery the N time circulation calculates formula and is:
The volume (L) of discharge energy (Wh)/the N time circulation of energy density (Wh/L)=the N time circulation of the N time circulation.
2. the circulation expansion rate test of lithium ion battery
At 25 DEG C, with 0.5C constant current by lithium ion cell charging to 4.35V, then with 4.35V constant-potential charge to electric current for 0.05C, survey cell thickness with height gage, thickness is now that battery completely fills thickness first; Then, with the constant current of 0.5C, lithium ion battery is discharged to 3.0V.By above charge and discharge system, after lithium ion battery the N time circulation is measured in 50 circulations, 100 circulations, 200 circulations after terminating, completely fill thickness respectively.
The circulation expansion rate of lithium ion battery is calculated as follows:
Circulation expansion rate (%)=[(after the N time circulation, completely filling thickness-completely fill thickness first)/completely fill thickness first] × 100%.
3. the capability retention test of lithium ion battery
At 25 DEG C, with the constant current of 0.5C by lithium ion cell charging to 4.35V, again with the constant-potential charge of 4.35V to electric current for 0.05C, then with the constant current of 0.5C, lithium ion battery is discharged to 3.0V, this discharge capacity is the discharge capacity first of lithium ion battery.By above charge and discharge system, test the N time cyclic discharge capacity.
The capability retention of lithium ion battery is calculated as follows:
Capability retention (%)=[the N time cyclic discharge capacity/discharge capacity first] × 100%.
Parameter and the performance test results of embodiment 1-7 lithium ion battery and comparative example 1-5 lithium ion battery are as shown in table 1.
From embodiment 1, 2, 3 with comparative example 1, 2, can find out in the contrast of 3, without the lithium ion battery of encapsulated blowing agent process, its circulation expansion rate is far longer than the lithium ion battery through encapsulated blowing agent process, the cycle performance of the lithium ion battery after encapsulated blowing agent process is also obviously promoted, this is because: be that the expansion of the first negative electrode active material provides space after blowing agent thermal decomposition, avoid the mutual extruding that the first negative electrode active material expands between the anode active material particles that causes, electrode structure is made to keep stable, ensure that electrical contact good between negative pole internal particle.
The parameter of table 1 embodiment 1-7 lithium ion battery and comparative example 1-5 lithium ion battery and the performance test results
The initial energy density of the lithium ion battery after encapsulated blowing agent process is compared with the initial energy density of the lithium ion battery without encapsulated blowing agent process, the former slightly reduces, this is because: the space that blowing agent occupies can make lithium ion battery lose part energy density, but the circulation expansion rate being through the lithium ion battery of encapsulated blowing agent process is reduced, discharge capacitance is improved, and therefore in fact the mean energy density of lithium ion battery obtains remarkable lifting.
From embodiment 1,4,5,6, can find out in the contrast of 7, along with the increase of blowing agent volume, the circulation expansion rate of lithium ion battery reduces gradually, and initial energy density also reduces gradually, this is because: when negative plate constancy of volume, along with the increase of blowing agent volume, larger space can be provided for the expansion of anode active material particles, the circulation expansion rate of lithium ion battery is reduced.But along with the increase of blowing agent volume, the volume of active material reduces, thus shows lithium ion battery initial energy density downward trend gradually.
From embodiment 4, 7 with comparative example 4, can find out in the contrast of 5, (the comparative example 4 when the volume that blowing agent accounts for the first negative electrode active material to reach 130% more than 120%, 130%), the circulation expansion rate of lithium ion battery reduces not obvious (relative to embodiment 4, 120%), but the initial energy density of lithium ion battery still can lose, this is because: the expansion space that blowing agent provides is much larger than the first negative electrode active material expansion requisite space, it expands to reduction circulation and does not obviously help, this part space but still can occupy a part of volume thus the initial energy density of lithium ion battery is reduced.When blowing agent account for the first negative electrode active material volume ratio too small time (comparative example 5,70%), the lifting of the initial energy density of lithium ion battery is very limited (compared to embodiment 7,80%), and the expansion rate that circulates is significantly increased, this is because: the space that blowing agent provides is too little, is not enough to expand to the first negative electrode active material, causes the obvious increase of circulation expansion rate.
In sum, the coated process of blowing agent is carried out to the first negative electrode active material, the circulation expansion rate of lithium ion battery can be effectively reduced, improve the cycle performance of lithium ion battery.When to account for the first negative electrode active material volume be 80%-120% to coated blowing agent, mean energy density can be obtained higher, the lithium ion battery that circulation expansion rate is less.
Relative to prior art, anode plate for lithium ionic cell of the present invention and preparation method thereof has the following advantages:
1. blowing agent is coated on the obvious first anode active material particles surface of volumetric expansion, through heat treatment, blowing agent decomposes, can be that the expansion of the first anode active material particles reserves enough spaces, extruding between the adjacent cathode active material particle that the expansion because of the first negative electrode active material can be avoided to cause, also the excessive bounce-back of cathode membrane can not be caused to expand, thus reduce expansion and the distortion of lithium ion battery, be conducive to keeping the unimpeded of whole electrodes conduct network, therefore the cycle performance of lithium ion battery can be improved, maintain the high-energy-density in circulating battery process.
2. optionally blowing agent is coated on volumetric expansion more obvious, the first anode active material particles surface that discharge capacity is higher, then it is mixed with material with carbon element, the discharge capacity of lithium ion battery can be improved, the energy density reduction that the equal encapsulated blowing agent of all negative electrode active materials causes can be avoided again.
The announcement of book and instruction according to the above description, those skilled in the art in the invention can also carry out suitable change and amendment to above-mentioned execution mode.Therefore, the present invention is not limited to embodiment disclosed and described above, also should fall in the protection range of claim of the present invention modifications and changes more of the present invention.In addition, although employ some specific terms in this specification, these terms just for convenience of description, do not form any restriction to the present invention.
Claims (11)
1. a preparation method for anode plate for lithium ionic cell, is characterized in that, comprises the following steps:
1) blowing agent is coated on the obvious first negative electrode active material surface of bulk effect, obtained the first negative electrode active material being coated with blowing agent;
2) by step 1) in obtained the first negative electrode active material being coated with blowing agent, material with carbon element, binding agent, conductive agent add in proportion and do not dissolve in the first solvent of blowing agent, obtain cathode size after fully stirring; And
3) by step 2) in obtained cathode size be spread evenly across on negative current collector, obtained negative plate after heat treatment removing blowing agent.
2. the preparation method of anode plate for lithium ionic cell according to claim 1, is characterized in that, step 1) in, described first negative electrode active material is one or more in silicon, tin, germanium, the simple substance of antimony, alloy or compound.
3. the preparation method of anode plate for lithium ionic cell according to claim 1, it is characterized in that, step 1) in, described blowing agent be selected from Celogen Az, azodiisobutyronitrile, N, N-dinitrosopentamethylene tetramine, benzene sulfonyl hydrazide, p-toluene sulfonylsemicarbazide one or more.
4. the preparation method of anode plate for lithium ionic cell according to claim 1, is characterized in that, step 1) in, described blowing agent volume is the 80%-120% of the first negative electrode active material volume.
5. the preparation method of anode plate for lithium ionic cell according to claim 1, is characterized in that, step 2) in, described first solvent is water.
6. the preparation method of anode plate for lithium ionic cell according to claim 1, is characterized in that, step 3) in, described heat treated temperature is 80-250 DEG C.
7. the preparation method of anode plate for lithium ionic cell according to claim 1, is characterized in that, step 1) in, described method blowing agent being coated on the first negative polarity material surface comprises:
Blowing agent and the first negative electrode active material are added in ball grinder;
Control ratio of grinding media to material, ball milling speed, ball milling interval leave standstill heat radiation time and Ball-milling Time, the first negative electrode active material that after ball milling, obtained blowing agent is coated.
8. the preparation method of anode plate for lithium ionic cell according to claim 1, is characterized in that, step 1) in, described method blowing agent being coated on the first negative electrode active material surface comprises:
Be dissolved in by blowing agent in the second solvent and obtain solution, wherein, the boiling point of the second solvent is lower than the decomposition temperature of blowing agent;
Appropriate first negative electrode active material is added in solution the acquisition suspension-turbid liquid that stirs; And
By suspension-turbid liquid atomization drying in spray dryer, the first negative electrode active material that obtained blowing agent is coated.
9. the preparation method of anode plate for lithium ionic cell according to claim 1, is characterized in that, step 1) in, described method blowing agent being coated on the first negative electrode active material surface comprises:
Blowing agent is dissolved in the second solvent and obtains solution;
First negative electrode active material to be added in solution and the acquisition suspension-turbid liquid that stirs;
Add in suspension-turbid liquid and do not dissolve blowing agent but the first solvent dissolved each other with the second solvent, in adition process, blowing agent is separated out gradually from solution, and is coated on the first negative electrode active material surface; And
Suspension-turbid liquid filtered, washs, obtain the first coated negative electrode active material of blowing agent after dry, grinding.
10. the preparation method of anode plate for lithium ionic cell according to claim 8 or claim 9, is characterized in that, described second solvent be selected from methyl-sulfoxide, methyl alcohol, ethanol, ether, acetone one or more.
11. 1 kinds of lithium ion batteries, comprise positive plate, negative plate, be interval in barrier film between positive plate and negative plate, and electrolyte, it is characterized in that, the negative plate that the preparation method that described negative plate is the anode plate for lithium ionic cell according to any one of claim 1-10 obtains.
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| CN107359353A (en) * | 2017-06-19 | 2017-11-17 | 佛山市大为科技有限公司 | A kind of modified lithium battery collection liquid surface coating waterborne conductive slurry and its preparation method and application |
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| CN103811719A (en) * | 2012-11-09 | 2014-05-21 | 华为技术有限公司 | Lithium ion battery silicon negative electrode plate and its preparation method and lithium ion battery |
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| JP2004063412A (en) * | 2002-07-31 | 2004-02-26 | Jfe Chemical Corp | Carbon material for negative electrode of lithium ion secondary battery and lithium ion secondary battery |
| CN103515607A (en) * | 2012-06-27 | 2014-01-15 | 比亚迪股份有限公司 | Negative electrode slurry of lithium ion battery, positive electrode of lithium ion battery prepared by slurry and battery |
| CN102931378A (en) * | 2012-10-09 | 2013-02-13 | 东莞市创明电池技术有限公司 | Lithium ion battery electrode, preparation method thereof and lithium ion battery |
| CN103811719A (en) * | 2012-11-09 | 2014-05-21 | 华为技术有限公司 | Lithium ion battery silicon negative electrode plate and its preparation method and lithium ion battery |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107359353A (en) * | 2017-06-19 | 2017-11-17 | 佛山市大为科技有限公司 | A kind of modified lithium battery collection liquid surface coating waterborne conductive slurry and its preparation method and application |
| CN107359353B (en) * | 2017-06-19 | 2019-04-23 | 佛山市大为科技有限公司 | A kind of modified lithium battery collection liquid surface coating waterborne conductive slurry and its preparation method and application |
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| CN105336917B (en) | 2018-11-20 |
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