CN105336917B - The preparation method of lithium ion battery and its negative electrode tab - Google Patents
The preparation method of lithium ion battery and its negative electrode tab Download PDFInfo
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- CN105336917B CN105336917B CN201410401790.4A CN201410401790A CN105336917B CN 105336917 B CN105336917 B CN 105336917B CN 201410401790 A CN201410401790 A CN 201410401790A CN 105336917 B CN105336917 B CN 105336917B
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The invention discloses a kind of preparation methods of anode plate for lithium ionic cell comprising following steps：1) foaming agent is coated on bulk effect apparent first negative electrode active material surface, the first negative electrode active material for being coated with foaming agent is made；2) the first negative electrode active material, carbon material, binder, the conductive agent obtained in step 1) for being coated with foaming agent is proportionally added into the first solvent of insoluble foaming agent, obtains negative electrode slurry after being sufficiently stirred；And 3) negative electrode slurry obtained in step 2) is spread evenly across on negative current collector, negative electrode tab is obtained after thermally treated removing foaming agent.In addition, the invention also discloses a kind of lithium ion batteries.Expansion of the lithium ion battery in charge and discharge process containing apparent first negative electrode active material of bulk effect in cathode can be effectively reduced in the preparation method of anode plate for lithium ionic cell of the present invention, the cycle performance for improving lithium ion battery, promotes the energy density of lithium ion battery.
Description
Technical field
The invention belongs to technical field of lithium ion, it is more particularly related to a kind of lithium ion battery and its
The preparation method of negative electrode tab, can reduce in cathode containing bulk effect significantly can embedding lithium active material lithium ion battery
Circulation expansion.
Background technique
In recent years, with smart phone, tablet computer, wearable device it is universal, to the energy of consumption Li-like ions battery
The requirement of metric density is also higher and higher.
Silicon substrate, tin-based material due to capacity it is big and de-/intercalation potential is low, be that next-generation lithium ion battery with high energy density is negative
The ideal material of pole active material.But such material is in de-/process of intercalation that there are serious volume expansion and contraction, meetings
It causes the destruction of material structure, the broken of active material particle and falls off from collector, cause lithium ion battery deformation, expansion
With the sharply deterioration of chemical property, therefore, it is difficult to be commercially available application.
In order to overcome drawbacks described above, a kind of effective method is by such capacity is big but the apparent material of bulk effect and carbon
Negative electrode tab is prepared as negative electrode active material after material mixing.It is above-mentioned compared with simple carbon material is as negative electrode active material
Mixing negative electrode active material is not only able to maintain good cycle performance, can also effectively improve discharge capacity, promotes energy density.
But when preparing negative electrode tab, volume change of different types of negative electrode active material during Li insertion extraction is inconsistent, example
Such as, silicon, tin-based active material volume change to be far longer than the volume change of carbon material, lead to the internal structure of negative electrode tab not
Stablize, therefore still cannot effectively inhibit the dilatancy after the long-term charge and discharge cycles of lithium ion battery.
In view of this, it is necessory to provide a kind of lithium ion battery that can effectively inhibit lithium ion battery dilatancy and
The preparation method of its negative electrode tab.
Summary of the invention
It is an object of the invention to：Overcoming the deficiencies of the prior art and provide one kind can effectively inhibit lithium ion battery swollen
The lithium ion battery of bulging deformation and its preparation method of negative electrode tab.
In order to achieve the above-mentioned object of the invention, the present invention provides a kind of preparation method of anode plate for lithium ionic cell, packets
Include following steps：
1) foaming agent is coated on bulk effect apparent first negative electrode active material surface, is made and is coated with foaming agent
First negative electrode active material；
2) by the first negative electrode active material, carbon material, binder, the conductive agent obtained in step 1) for being coated with foaming agent
It is proportionally added into the first solvent of insoluble foaming agent, obtains negative electrode slurry after being sufficiently stirred；And
3) negative electrode slurry obtained in step 2) is spread evenly across on negative current collector, drying, standing, cold pressing, heat
Processing obtains negative electrode tab after removing foaming agent.
A kind of improvement of preparation method as anode plate for lithium ionic cell of the present invention, first negative electrode active material are
Silicon (Si), tin (Sn), germanium (Ge), antimony (Sb) one of simple substance, alloy or compound or a variety of, the alloy, which refers to, includes
The alloy of at least one of silicon, tin, germanium or antimony element, the compound refer to comprising at least one of silicon, tin, germanium or antimony element
Compound.
A kind of improvement of preparation method as anode plate for lithium ionic cell of the present invention, the foaming agent are selected from azo diformazan
Amide, azodiisobutyronitrile, N, one of N- dinitrosopentamethylene tetramine, benzene sulfonyl hydrazide, p-toluene sulfonylsemicarbazide
Or it is a variety of.
A kind of improvement of preparation method as anode plate for lithium ionic cell of the present invention, the foaming agent volume are first negative
The 80%-120% of pole active material volume.
A kind of improvement of preparation method as anode plate for lithium ionic cell of the present invention, first solvent are water.
A kind of improvement of preparation method as anode plate for lithium ionic cell of the present invention, the temperature of the heat treatment are 80-
250℃.The temperature of heat treatment needs the decomposition temperature higher than foaming agent, can just make gap occur around the first active material, be
First active material provides expansion space.
A kind of improvement of preparation method as anode plate for lithium ionic cell of the present invention, it is described that foaming agent is coated on first
The method of negative polarity material surface includes：
1) foaming agent and the first negative electrode active material are added in ball grinder；
2) ratio of grinding media to material, ball milling speed, ball milling interval standing heat dissipation time and Ball-milling Time are controlled, foaming agent is made after ball milling
First negative electrode active material of cladding.
A kind of improvement of preparation method as anode plate for lithium ionic cell of the present invention, the ratio of grinding media to material are 3:1-5:1.
A kind of improvement of preparation method as anode plate for lithium ionic cell of the present invention, the ball milling speed are 500-
800r/min。
A kind of improvement of preparation method as anode plate for lithium ionic cell of the present invention, when the ball milling interval stands heat dissipation
Between for every 2 hours heat dissipation 30min.
A kind of improvement of preparation method as anode plate for lithium ionic cell of the present invention, the Ball-milling Time are 8-12h.
If ball milling speed is excessively high, overlong time will greatly increase the specific surface area of active material, cause battery in charge and discharge
Side reaction aggravates in electric process, deteriorates cycle performance；If ball milling speed is too small, the time is too short, then foaming agent is not able to achieve packet
It covers or coats not exclusively.
A kind of improvement of preparation method as anode plate for lithium ionic cell of the present invention, it is described that foaming agent is coated on first
The method on negative electrode active material surface includes：
1) foaming agent is dissolved in the second solvent and obtains solution, wherein point of the boiling point of the second solvent lower than foaming agent
Solve temperature, to avoid in spray-drying process foaming agent decompose；
2) appropriate first negative electrode active material is added in the solution prepared in step 1) and stirs evenly acquisition suspension；With
And
3) by suspension atomization drying in spray dryer obtained in step 2), first that foaming agent cladding is made is negative
Pole active material.
The boiling point of a kind of improvement of preparation method as anode plate for lithium ionic cell of the present invention, second solvent is lower than
20 DEG C of decomposition temperature or more of foaming agent.
A kind of improvement of preparation method as anode plate for lithium ionic cell of the present invention, it is described that foaming agent is coated on first
The method on negative electrode active material surface includes：
1) foaming agent is dissolved in the second solvent and obtains solution；
2) the first negative electrode active material is added in step 1) in solution obtained and stirs evenly acquisition suspension；
3) insoluble foaming agent is added in suspension obtained into step 2) but dissolves each other with the second solvent in step 1)
The first solvent, during the addition process, foaming agent is gradually precipitated from solution, and is coated on the first negative electrode active material surface；
And
4) suspension obtained in step 3) filtered, washed, is dry, obtaining the first cathode of foaming agent cladding after grinding
Active material.
A kind of improvement of preparation method as anode plate for lithium ionic cell of the present invention, it is sub- that second solvent is selected from diformazan
One of sulfone, methanol, ethyl alcohol, ether, acetone are a variety of.
In addition, the present invention also provides a kind of lithium ion batteries comprising positive plate, negative electrode tab, be interval in positive plate and
Isolation film and electrolyte between negative electrode tab, wherein negative electrode tab is the preparation method according to aforementioned anode plate for lithium ionic cell
Negative electrode tab obtained.
Compared with the existing technology, the preparation method of lithium ion battery of the present invention and its negative electrode tab has the following advantages that：
1. foaming agent is coated on volume expansion apparent first anode active material particles surface, thermally treated, foaming
Agent is thermally decomposed, and can be reserved enough spaces for the expansion of the first anode active material particles, be can avoid because of the first cathode
Extruding between adjacent cathode active material particle caused by the expansion of active material will not cause the excessive anti-of cathode membrane
Bullet expansion, to reduce the expansion and deformation of lithium ion battery, is conducive to keep the unimpeded of entire electrodes conduct network, therefore can
Improve the cycle performance of lithium ion battery, maintains the high-energy density during circulating battery.
2. selectively by foaming agent be coated on volume expansion become apparent, higher first negative electrode active material of discharge capacity
Then matter particle surface mixes it with carbon material, can improve the discharge capacity of lithium ion battery and all negative
Energy density caused by the equal encapsulated blowing agent of pole active material reduces.
Embodiment
In order to be more clear goal of the invention of the invention, technical solution and technical effect, with reference to embodiments and compare
Compared with example, the present invention is described in more detail.It should be understood that embodiment described in this specification is intended merely to explain this
Invention, be not intended to limit the present invention, formula, ratio of embodiment etc. can adaptation to local conditions make a choice and essence had no to result
Property influence.
It should be noted that the present invention includes first coating to foam on bulk effect apparent first negative electrode active material surface
The preprocessing process of agent, used foaming agent need not dissolved by the first solvent in negative electrode slurry whipping process, i.e. solubility
It is after the heat treatment apparent first negative electrode active of bulk effect to reach coated foaming agent lower than 0.01g/100ml
The purpose of mass expansion reserved space.
In addition, the foaming agent volume that the present invention coats is the 80%-120% of the first negative electrode active material volume, work as cladding
Foaming dosage it is very little when, sufficient space can not be reserved to the expansion of the first negative electrode active material, be easy to cause negative pole structure
It is unstable, cause biggish cell expansion and deformation.When the foaming agents content of cladding is excessive, reserved space has exceeded
The shared space of first negative electrode active material expansion, causes the waste in cathode space and the reduction of battery energy density.
Embodiment 1
1. preparing the first negative electrode active material of foaming agent cladding
1) azodicarbonamide is dissolved in dimethyl sulfoxide, prepares two formyl of azo that mass percentage is 3.5%
Amine aqueous solution；
2) acquisition suspension will be stirred evenly in solution obtained in appropriate SiO powder addition step 1), wherein azo two
The volume of formamide is the 100% of SiO volume；
3) azodicarbonamide cladding is made after being spray-dried suspension obtained in step 2) at 190 DEG C
SiO。
2. preparing anode plate for lithium ionic cell
1) by artificial graphite, azodicarbonamide coat SiO, polyacrylic acid (PAA), sodium carboxymethylcellulose (CMC),
Conductive carbon (SP) is added in appropriate amount of deionized water, artificial graphite：SiO (does not include foaming agent quality)：PAA：CMC：The quality of SP
Than being 81：9：7：1：2, it is stirred evenly at 30 DEG C, obtains the negative electrode slurry that solid content is 42%；
2) negative electrode slurry obtained in step 1) is spread evenly across on negative current collector copper foil, through 100 DEG C of dryings
30min, 30 tons of pressure are cold-pressed, and vacuum heat treatment 2h removes azodicarbonamide at 200 DEG C, obtains negative electrode tab.
3. preparing based lithium-ion battery positive plate
By positive active material LiCoO2, conductive carbon SP, binder Kynoar (PVDF) in mass ratio 95：2：3
It is uniformly mixed in solvent N-methyl pyrilidone (NMP) and the anode sizing agent that solid content is 70% is made, anode sizing agent is uniformly applied
It overlays on plus plate current-collecting body aluminium foil, the dry 30min at 110 DEG C, positive plate is made after cold pressing and slice.
4. preparing lithium-ion battery electrolytes
Ethylene carbonate (EC), propene carbonate (PC), methyl ethyl carbonate (DEC), fluorinated ethylene carbonate (FEC) are pressed
Mass ratio 25：25：45：5 are sufficiently mixed, and solute lithium hexafluoro phosphate (LiPF is added6), LiPF6Concentration is 1.1mol/L, and lithium is made
Ion battery electrolyte.
5. preparing lithium ion battery
By based lithium-ion battery positive plate made above, negative electrode tab, polyethylene (PE) isolation film by winding and encapsulation system
The lithium ion battery for being 80mm at thickness about 4mm, width 35mm, length, injects electrolyte after vacuum bakeout 12h at 75 DEG C
And it stands for 24 hours；Then, at 35 DEG C with the constant current charging of 0.1C to 4.35V, then extremely with 4.35V constant voltage charging
Electric current drops to 0.05C, is discharged to 3.0V with the constant current of 0.5C, is repeated 2 times charge and discharge, finally with the constant current of 0.5C
Lithium ion battery is charged into 3.85V, completes the preparation of lithium ion battery.
Embodiment 2
1. preparing the first negative electrode active material of foaming agent cladding
1) azodicarbonamide is dissolved in dimethyl sulfoxide, prepares two formyl of azo that mass percentage is 2.5%
Amine aqueous solution；
2) it will be stirred evenly in solution obtained in appropriate SiO powder addition step 1), make the volume of azodicarbonamide
It is the 100% of SiO volume；
3) water is slowly added dropwise in suspension obtained into step 2) and is stirred continuously, until amount of water and dimethyl sulfoxide matter
Measure equal, during the addition process, foaming agent is gradually precipitated from solution, is coated on the surface SiO；
4) suspension obtained in step 3) filtered, washed, is dry, obtaining azodicarbonamide cladding after grinding
SiO。
2. preparing based lithium-ion battery positive plate
Positive active material uses ternary material LiNi(1/3)Co(1/3)Mn(1/3)O2, by it with conductive carbon (SP), gather inclined fluorine
Ethylene (PVDF) in mass ratio 94：2：4 stir evenly in solvent N-methyl pyrilidone (NMP), and it is 70% that solid content, which is made,
Anode sizing agent, anode sizing agent is uniformly coated on plus plate current-collecting body aluminium foil, dry 30min, is cold-pressed and cuts at 110 DEG C
Positive plate is made after piece.
It prepares anode plate for lithium ionic cell, prepare lithium-ion battery electrolytes, and prepare the same embodiment of lithium ion battery
1。
Embodiment 3
1. preparing the first negative electrode active material of foaming agent cladding
1) by foaming agent azodiisobutyronitrile and Sn51Si30C19Alloy powder by volume 1：1 is added in ball grinder；
2) ball-milling material is zirconium oxide, ratio of grinding media to material 5：1, rotational speed of ball-mill 600r/min, every ball milling 2h stop ball milling
The Sn of azodiisobutyronitrile cladding is made after ball milling by 30min, Ball-milling Time 10h51Si30C19Alloy material.
2. preparing anode plate for lithium ionic cell
1) Sn for coating artificial graphite, azodiisobutyronitrile51Si30C19Alloy, butadiene-styrene rubber (SBR), carboxymethyl cellulose
Plain sodium (CMC), conductive carbon (SP) mixing, artificial graphite：Sn51Si30C19Alloy (disregards foaming agent quality)：SBR：CMC：SP's
Mass ratio is 81：9：6：2：2, it is stirred evenly at 30 DEG C after suitable quantity of water is added, obtains the negative electrode slurry that solid content is 45%；
2) negative electrode slurry obtained in step 1) is spread evenly across on negative current collector copper foil, through 60 DEG C of dry 20min,
30 tons of pressure are cold-pressed, and vacuum heat treatment 2h obtains negative electrode tab after removing azodiisobutyronitrile at 80 DEG C.
Based lithium-ion battery positive plate is prepared, lithium-ion battery electrolytes is prepared, prepares lithium ion battery with embodiment 1.
Embodiment 4
Lithium ion battery is prepared according to the method for embodiment 1, the difference is that only：Prepare foaming agent cladding first is negative
When the active material of pole, the volume of azodicarbonamide is the 120% of SiO volume.
Embodiment 5
Lithium ion battery is prepared according to the method for embodiment 1, the difference is that only：Prepare foaming agent cladding first is negative
When the active material of pole, the volume of azodicarbonamide is the 110% of SiO volume.
Embodiment 6
Lithium ion battery is prepared according to the method for embodiment 1, the difference is that only：Prepare foaming agent cladding first is negative
When the active material of pole, the volume of azodicarbonamide is the 90% of SiO volume.
Embodiment 7
Lithium ion battery is prepared according to the method for embodiment 1, the difference is that only：Prepare foaming agent cladding first is negative
When the active material of pole, the volume of azodicarbonamide is the 80% of SiO volume.
Comparative example 1
Lithium ion battery is prepared according to the method for embodiment 1, the difference is that only：It eliminates negative first in step 1)
Pole active material surface encapsulated blowing agent, the i.e. uncoated azodicarbonamide in the surface SiO.
Comparative example 2
Lithium ion battery is prepared according to the method for embodiment 2, the difference is that only：It eliminates negative first in step 1)
Pole active material surface encapsulated blowing agent, the i.e. uncoated azodicarbonamide in the surface SiO.
Comparative example 3
Lithium ion battery is prepared according to the method for embodiment 3, the difference is that only：It eliminates negative first in step 1)
Pole active material surface encapsulated blowing agent, i.e. Sn51Si30C19The uncoated azodiisobutyronitrile of alloy surface.
Comparative example 4
Lithium ion battery is prepared according to the method for embodiment 1, the difference is that only：Prepare foaming agent cladding first is negative
When the active material of pole, the volume of azodicarbonamide is the 130% of SiO volume.
Comparative example 5
Lithium ion battery is prepared according to the method for embodiment 1, the difference is that only：Prepare foaming agent cladding first is negative
When the active material of pole, the volume of azodicarbonamide is the 70% of SiO volume.
Performance of lithium ion battery test
1. lithium ion battery energy density is tested
At 25 DEG C, lithium ion battery is charged to by 4.35V with 0.5C constant current, then fill with the constant voltage of 4.35V
Electricity to electric current is 0.05C, tests the volume (L) of lithium ion battery；Then, with the constant current of 0.5C by lithium-ion electric tank discharge
To 3.0V, the discharge energy tested is initial discharge energy (Wh), and the energy density being calculated is first energy density.
In the above manner, the discharge energy (Wh) and volume (L) of the 50th time, 100 times, 200 times circulation of test lithium ion battery, calculates
The energy density (Wh/L) of 50th time, 100 times, 200 times circulation.
The energy density of lithium ion battery n-th circulation calculates formula：
The energy density (Wh/L) of n-th circulation=n-th circulation discharge energy (Wh)/n-th circulation volume
(L)。
2. the circulation expansion rate of lithium ion battery is tested
At 25 DEG C, lithium ion battery is charged to by 4.35V with 0.5C constant current, then with 4.35V constant voltage charging
To electric current be 0.05C, with high metric survey cell thickness, at this time completely fill thickness for the first time with a thickness of battery；Then, with the perseverance of 0.5C
Lithium ion battery is discharged to 3.0V by constant current.By the above charge and discharge system, respectively in 50 circulations, 100 circulations, 200 times
Thickness is completely filled after measurement lithium ion battery n-th circulation after circulation terminates.
The circulation expansion rate of lithium ion battery is calculated as follows：
Circulation expansion rate (%)=[(completely fill thickness-after n-th circulation and completely fill thickness for the first time)/thickness is completely filled for the first time] ×
100%.
3. the capacity retention ratio of lithium ion battery is tested
At 25 DEG C, lithium ion battery is charged to by 4.35V with the constant current of 0.5C, then with the constant voltage of 4.35V
Charging to electric current is 0.05C, lithium ion battery is then discharged to 3.0V with the constant current of 0.5C, this discharge capacity is
The discharge capacity for the first time of lithium ion battery.By the above charge and discharge system, n-th cyclic discharge capacity is tested.
The capacity retention ratio of lithium ion battery is calculated as follows：
Capacity retention ratio (%)=[n-th cyclic discharge capacity/for the first time discharge capacity] × 100%.
The parameter and the performance test results of embodiment 1-7 lithium ion battery and comparative example 1-5 lithium ion battery such as 1 institute of table
Show.
From embodiment 1,2,3 and Comparative Examples 1 and 2,3 comparison in as can be seen that the lithium handled without encapsulated blowing agent from
Sub- battery, circulation expansion rate are far longer than the lithium ion battery handled by encapsulated blowing agent, handle by encapsulated blowing agent
The cycle performance of lithium ion battery afterwards is also obviously improved, this is because：It is the first negative electrode active after foaming agent thermal decomposition
The expansion of substance provides space, avoids the phase between anode active material particles caused by the expansion of the first negative electrode active material
It mutually squeezes, makes electrode structure keep stablizing, ensure that good electrical contact between cathode internal particle.
The parameter and the performance test results of table 1 embodiment 1-7 lithium ion battery and comparative example 1-5 lithium ion battery
It is handled by the initial energy density of encapsulated blowing agent treated lithium ion battery with without encapsulated blowing agent
The initial energy density of lithium ion battery compare, the former slightly reduces, this is because：The space that foaming agent occupies can make lithium from
Sub- battery loses part energy density, but the circulation expansion rate for passing through the lithium ion battery of encapsulated blowing agent processing is dropped
Low, discharge capacitance is improved, therefore the mean energy density of lithium ion battery has been actually get and has been obviously improved.
It can be seen that the increase with foaming agent volume from embodiment Isosorbide-5-Nitrae, 5,6,7 comparison, lithium ion battery follows
Ring expansion rate gradually decreases, and initial energy density is gradually lowered, this is because：In the case where negative electrode tab constancy of volume, with
The increase of foaming agent volume, bigger space can be provided for the expansion of anode active material particles, make lithium ion battery
Circulation expansion rate is reduced.But with the increase of foaming agent volume, the volume of active material reduces, to show lithium
The trend that ion battery initial energy density is gradually reduced.
From the comparison of embodiment 4,7 and comparative example 4,5 as can be seen that when foaming agent accounts for the body of the first negative electrode active material
When product reaches 130% more than 120% (comparative example 4,130%), the circulation expansion rate of lithium ion battery reduces unobvious (phase
For embodiment 4,120%), but the initial energy density of lithium ion battery can still lose, this is because：What foaming agent provided
Expansion space has been much larger than space needed for the first negative electrode active material expands, and has not obviously helped to circulation expansion is reduced
It helps, this segment space can still occupy a part of volume but to make the initial energy density of lithium ion battery reduce.Work as foaming
Agent account for the first negative electrode active material volume ratio it is too small when (comparative example 5,70%), the promotion of the initial energy density of lithium ion battery
Very limited (compared to embodiment 7,80%), and recycle expansion rate and be significantly increased, this is because：The sky that foaming agent provides
Between it is too small, be not enough to give the expansion of first negative electrode active material, circulation expansion rate caused to significantly increase.
In conclusion carrying out the processing of foaming agent cladding to the first negative electrode active material, lithium ion battery can be effectively reduced
Circulation expansion rate, improve the cycle performance of lithium ion battery.It is when the foaming agent of cladding accounts for the first negative electrode active material volume
When 80%-120%, available mean energy density is higher, recycles the lesser lithium ion battery of expansion rate.
Compared with the existing technology, anode plate for lithium ionic cell of the present invention and preparation method thereof has the following advantages that：
1. foaming agent is coated on volume expansion apparent first anode active material particles surface, thermally treated, foaming
Agent is thermally decomposed, and can be reserved enough spaces for the expansion of the first anode active material particles, be can avoid because of the first cathode
Extruding between adjacent cathode active material particle caused by the expansion of active material will not cause the excessive anti-of cathode membrane
Bullet expansion, to reduce the expansion and deformation of lithium ion battery, is conducive to keep the unimpeded of entire electrodes conduct network, therefore can
Improve the cycle performance of lithium ion battery, maintains the high-energy density during circulating battery.
2. foaming agent is selectively coated on volume expansion to become apparent, higher first negative electrode active material of discharge capacity
Then matter particle surface mixes it with carbon material, can improve the discharge capacity of lithium ion battery and all negative
Energy density caused by the equal encapsulated blowing agent of pole active material reduces.
According to the disclosure and teachings of the above specification, those skilled in the art in the invention can also be to above-mentioned embodiment party
Formula carries out change and modification appropriate.Therefore, the invention is not limited to the specific embodiments disclosed and described above, to this
Some modifications and changes of invention should also be as falling into the scope of the claims of the present invention.In addition, although this specification
In use some specific terms, these terms are merely for convenience of description, does not limit the present invention in any way.
Claims (10)
1. a kind of preparation method of anode plate for lithium ionic cell, which is characterized in that include the following steps：
1) foaming agent is coated on bulk effect apparent first negative electrode active material surface, is made and is coated with the first of foaming agent
Negative electrode active material；The foaming agent is selected from azodicarbonamide, azodiisobutyronitrile, N, N- dinitroso pentamethylene four
One of amine, benzene sulfonyl hydrazide, p-toluene sulfonylsemicarbazide are a variety of；The foaming agent volume is the first negative electrode active material plastid
Long-pending 80%-120%；
2) by the first negative electrode active material obtained in step 1) for being coated with foaming agent, carbon material, binder, conductive agent by than
Example is added in the first solvent of insoluble foaming agent, obtains negative electrode slurry after being sufficiently stirred；And
3) negative electrode slurry obtained in step 2) is spread evenly across on negative current collector, is made after thermally treated removing foaming agent
Negative electrode tab.
2. the preparation method of anode plate for lithium ionic cell according to claim 1, which is characterized in that described in step 1)
First negative electrode active material is one of silicon, tin, germanium, the simple substance of antimony, alloy or compound or a variety of, and the alloy, which refers to, includes
The alloy of at least one of silicon, tin, germanium or antimony element, the compound refer to comprising at least one of silicon, tin, germanium or antimony element
Compound.
3. the preparation method of anode plate for lithium ionic cell according to claim 1, which is characterized in that described in step 2)
First solvent is water.
4. the preparation method of anode plate for lithium ionic cell according to claim 1, which is characterized in that described in step 3)
The temperature of heat treatment is 80-250 DEG C.
5. the preparation method of anode plate for lithium ionic cell according to claim 1, which is characterized in that described in step 1)
Include by the method that foaming agent is coated on the first negative polarity material surface：
Foaming agent and the first negative electrode active material are added in ball grinder；
Ratio of grinding media to material, ball milling speed, ball milling interval standing heat dissipation time and Ball-milling Time are controlled, foaming agent cladding is made after ball milling
First negative electrode active material.
6. the preparation method of anode plate for lithium ionic cell according to claim 1, which is characterized in that described in step 1)
Include by the method that foaming agent is coated on the first negative electrode active material surface：
Foaming agent is dissolved in the second solvent and obtains solution, wherein the boiling point of the second solvent is lower than the decomposition temperature of foaming agent；
Appropriate first negative electrode active material is added in solution and stirs evenly acquisition suspension；And
By suspension in spray dryer atomization drying, be made foaming agent cladding the first negative electrode active material.
7. the preparation method of anode plate for lithium ionic cell according to claim 6, which is characterized in that the second solvent choosing
From one of dimethyl sulfoxide, methanol, ethyl alcohol, ether, acetone or a variety of.
8. the preparation method of anode plate for lithium ionic cell according to claim 1, which is characterized in that described in step 1)
Include by the method that foaming agent is coated on the first negative electrode active material surface：
Foaming agent is dissolved in the second solvent and obtains solution；
First negative electrode active material is added in solution and stirs evenly acquisition suspension；
The first solvent that insoluble foaming agent is added into suspension but dissolves each other with the second solvent, during the addition process, foaming agent
It is gradually precipitated from solution, and is coated on the first negative electrode active material surface；And
Suspension is filtered, is washed, is dry, obtains the first negative electrode active material of foaming agent cladding after grinding.
9. the preparation method of anode plate for lithium ionic cell according to claim 8, which is characterized in that the second solvent choosing
From one of dimethyl sulfoxide, methanol, ethyl alcohol, ether, acetone or a variety of.
10. a kind of lithium ion battery, including positive plate, negative electrode tab, the isolation film being interval between positive plate and negative electrode tab, and
Electrolyte, which is characterized in that the negative electrode tab is according to anode plate for lithium ionic cell of any of claims 1-9
Negative electrode tab made from preparation method.
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| CN201410401790.4A CN105336917B (en) | 2014-08-14 | 2014-08-14 | The preparation method of lithium ion battery and its negative electrode tab |
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| 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 |
| 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 |
| 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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| 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 |
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