CN105304858B - Lithium ion battery and its negative plate and preparation method - Google Patents
Lithium ion battery and its negative plate and preparation method Download PDFInfo
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- CN105304858B CN105304858B CN201410326711.8A CN201410326711A CN105304858B CN 105304858 B CN105304858 B CN 105304858B CN 201410326711 A CN201410326711 A CN 201410326711A CN 105304858 B CN105304858 B CN 105304858B
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The present invention provides a kind of lithium ion battery and its negative plate and preparation method.The negative plate includes negative current collector；And cathode membrane, it is arranged on negative current collector and comprising negative active core-shell material, negative pole with binding agent and negative pole conductive agent.Negative active core-shell material includes silicon-based active material and carbon-based active material；The surface distributed of negative active core-shell material has negative pole binding agent；Contain OH in the surface of silicon-based active material；Negative pole is comprised at least with binding agent contains COOM binding agents；The negative pole binding agent of silicon-based active material surface distributed and the mass ratio of silicon-based active material are more than the negative pole binding agent of carbon-based active material surface distributed and the mass ratio of carbon-based active material.The negative plate of the present invention had both improved cohesive force between the particle of silicon-based active material, can improve the problem of charge-discharge performance of the excessive caused carbon-based active material of negative pole binding agent deteriorates again.The lithium ion battery of the present invention has good low temperature performance and high temperature cyclic performance.
Description
Technical field
The present invention relates to cell art, more particularly to a kind of lithium ion battery and its negative plate and preparation method.
Background technology
Because lithium ion battery has the characteristics that energy density height, long lifespan, self discharge be low, memory-less effect, therefore quilt
It is widely used in the portable type electronic products such as mobile phone, notebook computer, digital camera.However, various portable type electronic products
Miniaturization, intelligent and multifunction fast development, higher requirement is proposed to the energy density of lithium ion battery.
At present, lithium ion battery mainly uses carbon-based active material based on graphite as negative active core-shell material, carbon-based
The relatively low gram volume of active material limits the further lifting of the energy density of lithium ion battery.With carbon-based active material phase
Than, silicon-based active material has very high gram volume, using silicon-based active material as the negative active core-shell material of lithium ion battery,
The energy density of lithium ion battery can be significantly improved.However, Volume Changes of the silicon-based active material in charge and discharge process are very
Greatly, its particle is easily broken crushing under huge stress, causes intergranular contact to be deteriorated, electric conductivity reduces, and then causes
Capacity sharp-decay after lithium ion battery circulation.Volume Changes of the carbon-based active material in charge and discharge process are much smaller than silicon substrate
Active material, silicon-based active material is mixed with carbon-based active material and mixes negative active core-shell material and can effectively alleviate charge and discharge
Volume Changes in electric process.But in the mixing negative active core-shell material of routine, binding agent is evenly distributed on carbon-based active material
On the surface of material and silicon-based active material.Lithium ion poor-performing is led due to binding agent, if the too high levels of binding agent, meeting
The charge-discharge performance of carbon-based active material is had a strong impact on, causes to occur to analyse the problems such as lithium, low temperature discharge capacity be low；If binding agent
Content it is too low, then can not bond and expand more serious silicon-based active material, cause the negative plate in charge and discharge process rebound compared with
Greatly, so lithium ion battery thickness swelling it is serious.
The content of the invention
In view of problem present in background technology, it is an object of the invention to provide a kind of lithium ion battery and its negative plate
And preparation method, the negative plate had both improved the cohesive force between the particle of silicon-based active material, negative pole use can be improved again
The problem of charge-discharge performance of the excessive caused carbon-based active material of binding agent deteriorates, the lithium ion battery have good low
Warm discharge performance and high temperature cyclic performance.
To achieve these goals, in the first aspect of the present invention, the invention provides a kind of negative pole of lithium ion battery
Piece, it includes：Negative current collector；And cathode membrane, it is arranged on negative current collector and is used comprising negative active core-shell material, negative pole
Binding agent and negative pole conductive agent.Negative active core-shell material includes silicon-based active material and carbon-based active material；Negative electrode active
The surface distributed of material has negative pole binding agent；Contain-OH in the surface of silicon-based active material；Negative pole binding agent, which comprises at least, to be contained
There is-COOM binding agent, wherein, the one kind of M in H, Li, Na, K, Mg, Al, Ca, Zn；Wherein, silicon-based active material surface
The negative pole that the negative pole binding agent of distribution and the mass ratio of silicon-based active material are more than carbon-based active material surface distributed bonds
Agent and the mass ratio of carbon-based active material.
In the second aspect of the present invention, the invention provides a kind of preparation method of the negative plate of lithium ion battery, it is used for
Prepare the negative plate of the lithium ion battery of first aspect present invention, including step：(1) by silicon-based active material, the first conductive agent,
First binding agent, which is proportionally added into solvent deionized water, to be uniformly mixed, and is adjusted pH value afterwards and is less than 7, heats up and hold afterwards
Continuous stirring makes the solid content of slurry reach setting, obtains the first slurry, wherein ,-OH is contained on the surface of silicon-based active material, the
One binding agent comprises at least the binding agent containing-COOM, wherein, the one kind of M in H, Li, Na, K, Mg, Al, Ca, Zn；(2)
Carbon-based active material, the second conductive agent, the second binding agent are proportionally added into solvent deionized water and be uniformly mixed, is obtained
Solid content is the second slurry of setting；(3) the first slurry and the second slurry are mixed and stirred for uniformly, obtaining mixed slurry,
Wherein, negative active core-shell material includes silicon-based active material and carbon-based active material, and the surface distributed of negative active core-shell material has negative
Pole binding agent, negative pole include the first binding agent and the second binding agent with binding agent, and negative pole includes the first conductive agent with conductive agent
With the second conductive agent, the negative pole binding agent of silicon-based active material surface distributed and the mass ratio of silicon-based active material are more than carbon-based
The negative pole binding agent of surface of active material distribution and the mass ratio of carbon-based active material；(4) mixed slurry is coated in negative pole
On collector, the negative plate of lithium ion battery is obtained after drying.
In the third aspect of the present invention, the invention provides a kind of lithium ion battery, and it includes：Positive plate；Negative plate；Every
From film, it is interval between positive plate and negative plate；And electrolyte.The negative plate be according to the lithium of first aspect present invention from
The negative plate of sub- battery.
Beneficial effects of the present invention are as follows：
The preparation method of the negative plate of the lithium ion battery of the present invention can realize negative pole binding agent in silicon-based active material
With the uneven distribution on carbon-based active material surface, and the negative pole binding agent of silicon-based active material surface distributed and silicon substrate are lived
Property material mass ratio be more than carbon-based active material surface distributed negative pole binding agent and carbon-based active material mass ratio, from
And the cohesive force between the particle of silicon-based active material can be improved, born caused by the expansion for the particle for suppressing silicon-based active material
The bounce-back of pole diaphragm, while can also make carbon-based active material that there is good chemical property, and then have lithium ion battery
There are good low temperature performance and high temperature cyclic performance.
Embodiment
The following detailed description of the lithium ion battery according to the present invention and its negative plate and preparation method and embodiment, compare
Example and test result.
Illustrate the negative plate of lithium ion battery according to a first aspect of the present invention first.
The negative plate of lithium ion battery according to a first aspect of the present invention, including：Negative current collector；And cathode membrane,
It is arranged on negative current collector and comprising negative active core-shell material, negative pole with binding agent and negative pole conductive agent.Negative electrode active material
Material includes silicon-based active material and carbon-based active material；The surface distributed of negative active core-shell material has negative pole binding agent；Silicon substrate
Contain-OH in the surface of active material；Negative pole with binding agent comprise at least containing-COOM binding agent, wherein, M be selected from H, Li,
One kind in Na, K, Mg, Al, Ca, Zn；Wherein, the negative pole binding agent of silicon-based active material surface distributed and silicon-based active material
The mass ratio of material is more than the negative pole binding agent of carbon-based active material surface distributed and the mass ratio of carbon-based active material.
In the negative plate of lithium ion battery described according to a first aspect of the present invention, the negative current collector can be copper
Paper tinsel.
In the negative plate of lithium ion battery described according to a first aspect of the present invention, the silicon-based active material may be selected from
Silicon, SiOx(0.6<x<1.5), the one or more in silicon/carbon complex.Wherein, the carbon in the silicon/carbon complex may be selected from
One kind in Delanium, native graphite, soft carbon, hard carbon, carbon fiber, carbonaceous mesophase spherules, CNT (CNT), graphene
It is or several.
In the negative plate of lithium ion battery described according to a first aspect of the present invention, the carbon-based active material may be selected from
One kind in Delanium, native graphite, hard carbon, soft carbon, carbon fiber, carbonaceous mesophase spherules, CNT (CNT), graphene
It is or several.
In the negative plate of lithium ion battery described according to a first aspect of the present invention, the negative pole binding agent can also wrap
Include the one or more in butadiene-styrene rubber, polyvinyl alcohol, POLYPROPYLENE GLYCOL.
In the negative plate of lithium ion battery described according to a first aspect of the present invention, the binding agent containing-COOM
May be selected from sodium carboxymethylcellulose (CMC), polyacrylic acid (PAA), polyacrylate (PAAM, wherein, M be selected from Li, Na, K, Mg,
One kind in Al, Ca, Zn), the one or more in sodium alginate (ALG).
Secondly the preparation method of the negative plate of the lithium ion battery of explanation according to a second aspect of the present invention.
The preparation method of the negative plate of lithium ion battery according to a second aspect of the present invention, for preparing first party of the present invention
The negative plate of the lithium ion battery in face, including step：(1) by silicon-based active material, the first conductive agent, the first binding agent in proportion
Add in solvent deionized water and be uniformly mixed, adjust pH value afterwards and be less than 7, heating up afterwards and continuing stirring makes consolidating for slurry
Content reaches setting, obtains the first slurry, wherein ,-OH is contained on the surface of silicon-based active material, and the first binding agent comprises at least
Binding agent containing-COOM, wherein, the one kind of M in H, Li, Na, K, Mg, Al, Ca, Zn；(2) by carbon-based active material,
Second conductive agent, the second binding agent are proportionally added into solvent deionized water and are uniformly mixed, and it is setting to obtain solid content
The second slurry；(3) the first slurry and the second slurry are mixed and stirred for uniformly, obtaining mixed slurry, wherein, negative electrode active material
Material includes silicon-based active material and carbon-based active material, and the surface distributed of negative active core-shell material has negative pole binding agent, negative pole
Include the first binding agent and the second binding agent with binding agent, negative pole includes the first conductive agent and the second conductive agent, silicon with conductive agent
The negative pole binding agent of based active material surface distributed and the mass ratio of silicon-based active material are more than carbon-based active material surface point
The negative pole binding agent of cloth and the mass ratio of carbon-based active material；(4) mixed slurry is coated on negative current collector, after drying
Obtain the negative plate of lithium ion battery.
In the preparation method of the negative plate of lithium ion battery described according to a second aspect of the present invention, the first slurry includes
Binding agent containing-COOM ,-COOM binding agent should be contained under sour environment, stirred by heating up, meeting and silicon-based active material
- the OH of the particle surface of material occurs esterification and produces chemical bond, and its effect is more stronger than physisorption, so as to make to contain
The binding agent for having-COOM is firmly bonded in the particle surface of silicon-based active material.When the first slurry mixes with the second slurry, by
Chemical bond between the particle of silicon-based active material and the binding agent containing-COOM be present, therefore the binding agent containing-COOM is not
It can be split away off from the particle surface of silicon-based active material, so as to which particle of the negative pole binding agent in silicon-based active material can be realized
With the uneven distribution on the particle of carbon-based active material, the bonding between the particle of silicon-based active material so can be both improved
Power, the bounce-back of cathode membrane caused by the expansion for the particle for suppressing silicon-based active material, while carbon-based active material can also be made
With good chemical property, final lithium ion battery has good low temperature performance and high temperature circulation simultaneously
Energy.
In the preparation method of the negative plate of lithium ion battery described according to a second aspect of the present invention, in step (1),
The mass ratio of the binding agent containing-COOM and silicon-based active material in first binding agent can be (1:99)~(10:90).
In the preparation method of the negative plate of lithium ion battery described according to a second aspect of the present invention, in step (1),
First binding agent may also include the one or more in butadiene-styrene rubber, polyvinyl alcohol, POLYPROPYLENE GLYCOL.
In the preparation method of the negative plate of lithium ion battery described according to a second aspect of the present invention, in step (1),
First conductive agent may be selected from the one or more in Super-P, conductive black, electrically conductive graphite.
In the preparation method of the negative plate of lithium ion battery described according to a second aspect of the present invention, in step (1),
Oxalic acid, acetic acid or citric acid regulation pH value can be used.
In the preparation method of the negative plate of lithium ion battery described according to a second aspect of the present invention, in step (1),
The pH value preferably can be 2~3.
In the preparation method of the negative plate of lithium ion battery described according to a second aspect of the present invention, in step (1),
The temperature of the heating can be 50 DEG C~70 DEG C.
In the preparation method of the negative plate of lithium ion battery described according to a second aspect of the present invention, in step (1),
The setting of the solid content of first slurry can be more than 65%, preferably can be 70%~80%.
In the preparation method of the negative plate of lithium ion battery described according to a second aspect of the present invention, in step (2),
Second binding agent may include the one or more in the binding agent containing-COOM, butadiene-styrene rubber, polyvinyl alcohol, POLYPROPYLENE GLYCOL.
In the preparation method of the negative plate of lithium ion battery described according to a second aspect of the present invention, in step (2),
The mass ratio of the binding agent containing-COOM and carbon-based active material in second binding agent can be (0:100)~(5:95).
In the preparation method of the negative plate of lithium ion battery described according to a second aspect of the present invention, in step (2),
Second conductive agent may be selected from the one or more in Super-P, conductive black, electrically conductive graphite.
In the preparation method of the negative plate of lithium ion battery described according to a second aspect of the present invention, in step (2),
The setting of the solid content of second slurry can be 30%~60%.
Illustrate lithium ion battery according to a third aspect of the present invention again.
Lithium ion battery according to a third aspect of the present invention, including：Positive plate；Negative plate；Barrier film, it is interval in positive plate
Between negative plate；And electrolyte.Wherein, the negative plate is the negative pole according to the lithium ion battery of first aspect present invention
Piece.
Next explanation is according to lithium ion battery and its embodiment and comparative example of negative plate and preparation method of the invention.
Embodiment 1
1. the preparation of the negative plate of lithium ion battery
(1) silicon grain, the first conductive agent Super P, the first binding agent molecular weight for being 3 μm by silicon-based active material D50
For 400000 polyacrylic acid in mass ratio 96:1:3 add in solvent deionized water, are thoroughly mixed uniformly, afterwards with grass
Acid regulation slurry pH value be 3, then slurry is slowly warming up to 60 DEG C and continue stirring until slurry solid content be 70%, obtain
To the first slurry, wherein ,-OH is contained on the surface of silicon grain；
(2) it is 15 μm of Delanium by carbon-based active material D50, the second conductive agent Super P, the second bonding agent molecule
Measure the polyacrylic acid in mass ratio 98 for 400000:1:1 adds in solvent deionized water, is thoroughly mixed uniformly, is formed solid
Content is 48% the second slurry；
(3) the second slurry is slowly added into the first slurry and is thoroughly mixed uniformly, obtain mixed slurry, its
In, in mixed slurry, the mass ratio of carbon-based active material and silicon-based active material is 90:10, wherein, negative active core-shell material bag
Silicon-based active material and carbon-based active material are included, the surface distributed of negative active core-shell material has negative pole binding agent, and negative pole is used viscous
Knot agent includes the first binding agent and the second binding agent, and negative pole includes the first conductive agent and the second conductive agent with conductive agent；
(4) mixed slurry is uniformly coated on the negative current collector copper foil of 8 μ m-thicks, through drying, compacting, cut-parts, slitting,
After soldering polar ear, the negative plate of lithium ion battery is obtained.
2. the preparation of the positive plate of lithium ion battery
It is 18 μm of cobalt acid lithium, positive pole conductive agent Super P, positive pole binding agent PVDF by positive electrode active materials D50
In mass ratio 96:2:2 are added in solvent NMP, and anode sizing agent is obtained after being thoroughly mixed uniformly, afterwards that anode sizing agent is uniform
It is coated on the plus plate current-collecting body aluminium foil of 14 μ m-thicks, after drying, compacting, cut-parts, slitting, soldering polar ear, obtains lithium-ion electric
The positive plate in pond.
3. the preparation of the electrolyte of lithium ion battery
The electrolyte of lithium ion battery is 1M lithium hexafluoro phosphate (LiPF6) for lithium salts using concentration, with ethylene carbonate
(EC), the mixture of diethyl carbonate (DEC) and methyl ethyl carbonate (EMC) is non-aqueous organic solvent, wherein each carbonic ester
Volume ratio is EC:DEC:EMC=1:1:1.
4. the preparation of lithium ion battery
By the positive plate, negative plate and barrier film (polyethylene, PE) of the lithium ion battery of preparation by winding and encapsulation
Technique is prepared into the battery core that thickness is 4.5mm, width 42mm, length are 61mm, afterwards the vacuum bakeout 10h at 75 DEG C, note
Enter electrolyte and stand 24h, obtain lithium ion battery.
Embodiment 2
Method according to embodiment 1 prepares lithium ion battery, except following difference：
1. the preparation of the negative plate of lithium ion battery
(1) silicon-based active material is the SiO1.1 that D50 is 3 μm, and-OH is contained on SiO1.1 surface, and the first binding agent is point
The Lithium polyacrylate that son amount is 800000；
(2) carbon-based active material is CNT, and the second binding agent is the Lithium polyacrylate that molecular weight is 800000.
Embodiment 3
Method according to embodiment 1 prepares lithium ion battery, except following difference：
1. the preparation of the negative plate of lithium ion battery
(1) silicon-based active material is silicon/Delanium compound that D50 is 3 μm, wherein, silicon/Delanium compound
- OH is contained on surface, and it is 20% that silicon, which is coated on the surface of Delanium and the mass fraction of silicon, and the first binding agent is that molecular weight is
600000 sodium alginate (ALG)；
(2) carbon-based active material is the hard carbon that D50 is 15 μm, and the second binding agent is the sodium alginate that molecular weight is 600000
(ALG)。
Embodiment 4
Method according to embodiment 1 prepares lithium ion battery, except following difference：
1. the preparation of the negative plate of lithium ion battery
(2) Delanium, the second conductive agent Super P, the poly- second of the second binding agent for being 15 μm by carbon-based active material D50
Enol in mass ratio 98:1:1 add solvent deionized water in, be thoroughly mixed uniformly, is formed solid content for 48% second
Slurry.
Embodiment 5
Method according to embodiment 1 prepares lithium ion battery, except following difference：
1. the preparation of the negative plate of lithium ion battery
(2) Delanium, the second conductive agent Super P, the second binding agent carboxylic first for being 15 μm by carbon-based active material D50
Base sodium cellulosate and butadiene-styrene rubber in mass ratio 97:1:1:1 adds in solvent deionized water, is thoroughly mixed uniformly, is formed
Solid content is 48% the second slurry.
Embodiment 6
Method according to embodiment 5 prepares lithium ion battery, except following difference：
1. the preparation of the negative plate of lithium ion battery
(1) silicon grain, the first conductive agent Super P, the first binding agent molecular weight for being 3 μm by silicon-based active material D50
Lithium polyacrylate and polyvinyl alcohol in mass ratio 95 for 800000:1:3:1 adds in solvent deionized water, is thoroughly mixed
Uniformly, afterwards with oxalic acid adjust slurry pH value be 3, then slurry is slowly warming up to 60 DEG C and continue stirring until consolidating for slurry
Content is 70%, obtains the first slurry.
Embodiment 7
Method according to embodiment 6 prepares lithium ion battery, except following difference：
1. the preparation of the negative plate of lithium ion battery
(1) first binding agent is sodium carboxymethylcellulose and butadiene-styrene rubber, silicon grain, Super P, carboxymethyl cellulose
Sodium, the mass ratio of butadiene-styrene rubber are 95:1:3:1.
Embodiment 8
Method according to embodiment 7 prepares lithium ion battery, except following difference：
1. the preparation of the negative plate of lithium ion battery
(1) silicon grain, Super P, sodium carboxymethylcellulose, the mass ratio of butadiene-styrene rubber are 93:1:5:1.
Embodiment 9
Method according to embodiment 7 prepares lithium ion battery, except following difference：
1. the preparation of the negative plate of lithium ion battery
(1) silicon grain, Super P, sodium carboxymethylcellulose, the mass ratio of butadiene-styrene rubber are 91:1:7:1.
Embodiment 10
Method according to embodiment 7 prepares lithium ion battery, except following difference：
1. the preparation of the negative plate of lithium ion battery
The pH value of (1) first slurry is 2.
Embodiment 11
Method according to embodiment 7 prepares lithium ion battery, except following difference：
1. the preparation of the negative plate of lithium ion battery
The pH value of (1) first slurry is 5.
Embodiment 12
Method according to embodiment 7 prepares lithium ion battery, except following difference：
1. the preparation of the negative plate of lithium ion battery
It is 65% that the warming temperature of (1) first slurry, which is 50 DEG C and continues stirring until the solid content of the first slurry,.
Embodiment 13
Method according to embodiment 7 prepares lithium ion battery, except following difference：
1. the preparation of the negative plate of lithium ion battery
It is 80% that the warming temperature of (1) first slurry, which is 70 DEG C and continues stirring until the solid content of the first slurry,.
Comparative example 1
Method according to embodiment 1 prepares lithium ion battery, except following difference：
1. the preparation of the negative plate of lithium ion battery
By the mixture of Delanium that negative active core-shell material D50 is 15 μm and silicon grain that D50 is 3 μm, (mass ratio is
90:10), negative pole conductive agent Super P, negative pole binding agent sodium carboxymethylcellulose and butadiene-styrene rubber in mass ratio 97:1:
1:1 adds in solvent deionized water, is thoroughly mixed the slurry for uniformly, forming that solid content is 48%, afterwards that slurry is uniform
Be on 8 μm of negative current collector copper foil coated in thickness, after drying, compacting, cut-parts, slitting, soldering polar ear, obtain lithium from
The negative plate of sub- battery.
Comparative example 2
Method according to comparative example 1 prepares lithium ion battery, except following difference：
1. the preparation of the negative plate of lithium ion battery
Negative active core-shell material, Super P, the mass ratio of sodium carboxymethylcellulose and butadiene-styrene rubber are 95:1:3:1.
Comparative example 3
Method according to embodiment 7 prepares lithium ion battery, except following difference：
1. the preparation of the negative plate of lithium ion battery
(1) pH value of the first slurry is not adjusted.
Comparative example 4
Method according to embodiment 7 prepares lithium ion battery, except following difference：
1. the preparation of the negative plate of lithium ion battery
(1) after adjusting pH value, without warming temperature, but in ambient operation.
Comparative example 5
Method according to embodiment 7 prepares lithium ion battery, except following difference：
1. the preparation of the negative plate of lithium ion battery
The solid content of (1) first slurry is 55%.
The lithium ion battery and its performance of negative plate and preparation method for finally providing embodiment 1-13 and comparative example 1-5 are surveyed
Examination process and test result.
(1) the cohesive force test of cathode membrane
Cathode membrane after cold pressing is prepared into the sample that length is 20cm, width is 15mm, surveyed on testing machine is drawn high
The cohesive force of cathode membrane is measured, wherein draw speed is 100mm/s.
(2) the bounce-back ratio test of negative plate
The thickness of negative plate after being cold-pressed with miking, is designated as T1；Afterwards by lithium ion battery at 25 DEG C with
0.7C multiplying powers constant-current charge takes lithium ion battery apart, and be designated as again with the thickness of miking negative plate afterwards to 3.85V
T2。
Bounce-back ratio (%)=(T of negative plate2-T1)/T1× 100%.
(3) the low temperature performance test of lithium ion battery
At 25 DEG C, by lithium ion battery with 0.7C multiplying powers constant-current charge to 4.20V, arrived afterwards with 4.20V constant-voltage charges
0.05C, then with 0.5C multiplying powers constant-current discharge to 3.0V, record the discharge capacity at 25 DEG C；Again by lithium ion battery with 0.7C
Multiplying power constant-current charge, afterwards with 4.20V constant-voltage charges to 0.05C, is then put to 4.20V at -10 DEG C with 0.5C multiplying power constant currents
Electricity arrives 3.0V, records the discharge capacity at -10 DEG C.
The discharge capacity at discharge capacity/25 DEG C at the low temperature discharge ratio (%) of lithium ion battery=- 10 DEG C ×
100%.
(4) the high temperature circulation expansion rate test of lithium ion battery
At 45 DEG C, by lithium ion battery with 0.7C multiplying powers constant-current charge to 4.20V, arrived afterwards with 4.20V constant-voltage charges
0.05C, the thickness of the lithium ion battery of fully charged state is measured, be designated as original depth, then arrived with 0.5C multiplying power constant-current discharges
3.0V, this is a charge and discharge cycles process；Expire when repeating above charge and discharge cycles process 300 times, and measuring the 300th circulation
The thickness of the lithium ion battery of charged state, the thickness being designated as after circulation.
The high temperature circulation expansion rate (%) of lithium ion battery=(thickness/original depth -1 after circulation) × 100%.
Table 1 provides embodiment 1-13 and comparative example 1-5 parameter and the performance test results.
Next embodiment 1-13 and comparative example 1-5 the performance test results are analyzed.
From embodiment 1-13 and comparative example 1-2 contrast as can be seen that with negative pole binding agent in carbon-based active material
Compared with the equally distributed comparative example 1-2 in silicon-based active material surface negative plate, negative pole binding agent of the invention is carbon-based
Active material and the negative plate of silicon-based active material surface uneven distribution have higher cathode membrane cohesive force and relatively low
Thickness bounce-back ratio, and then lithium ion battery has preferable low temperature performance and high temperature cyclic performance.This is due at this
In the negative plate that the preparation method of invention obtains, negative pole binding agent uneven distribution on negative active core-shell material, and silicon substrate is lived
Property the negative pole binding agent of material surface distribution and the mass ratio of silicon-based active material be more than carbon-based active material surface distributed
The mass ratio of negative pole binding agent and carbon-based active material, between the particle that can so improve silicon-based active material well
Cohesive force, the bounce-back of cathode membrane caused by the expansion for the particle for suppressing silicon-based active material, while and can avoids carbon-based active
The problem of low temperature discharge capacity step-down of the too high caused lithium ion battery of negative pole binder content of material surface, so that
Carbon-based active material has good chemical property, and then lithium ion battery has good low temperature performance and high temperature
Cycle performance.
When the binding agent containing-COOM added when preparing slurry is 1% (comparative example 1), due to silicon-based active material
The binding agent containing-COOM on surface is very few (i.e. the negative pole binding agent on silicon-based active material surface is very few), causes negative electrode film
The cohesive force of piece is too low, be not enough to suppress silicon-based active material expansion, and then negative plate thickness bounce-back large percentage, lithium from
Thickness swelling after sub- battery high-temperature circulation is serious.(the ratio when binding agent containing-COOM added when preparing slurry is 3%
Compared with example 2), although the cohesive force increase of cathode membrane, the thickness bounce-back ratio of negative plate reduces, after high-temperature lithium ion battery circulation
Thickness swelling reduce, but lithium ion battery low temperature discharge ratio is greatly reduced.This is due to that negative pole is absorbed with binding agent
Electrolyte and transmission lithium ion poor-performing, and carbon-based active material surface it is too high the binding agent containing-COOM it is (i.e. carbon-based
The too high levels of the negative pole binding agent of surface of active material), the interface impedance of negative pole is added, so as to cause lithium ion battery
Low temperature performance be deteriorated.
As can be seen that binding agent containing-COOM with silicon-based active material surface from embodiment 7-9 contrast
Weight/mass percentage composition increase (i.e. the weight/mass percentage composition increase of the negative pole binding agent on silicon-based active material surface), cathode membrane
Cohesive force increase, the thickness bounce-back ratio of negative plate reduces, and lithium ion battery thickness swelling at high temperature reduces, still
The low temperature performance of lithium ion battery is deteriorated.This is due to that excessive negative pole binding agent can be to the power of silicon-based active material
Learn performance to have a negative impact, while the excessive binding agent containing-COOM can not be pinned at silicon-based active material table completely
Face, in mixed slurry preparation process, the excessive binding agent containing-COOM can be transferred to carbon-based active material surface, so as to
Influence the low temperature performance of carbon-based active material.
As can be seen that the increase of the pH value with the first slurry, negative pole from embodiment 7 and embodiment 10-11 contrast
The cohesive force of diaphragm gradually reduces, and the thickness bounce-back ratio increase of negative plate, the low temperature discharge ratio of lithium ion battery first increases
After reduce, the thickness swelling of lithium ion battery at high temperature gradually increases, therefore the pH value of the first slurry should be moderate.From reality
Apply in the contrast of example 7 and comparative example 3 and can also be seen that due to the pH value of the first slurry not being adjusted in comparative example 3, because
The performance of this negative plate and lithium ion battery is poor.
From embodiment 7 and embodiment 12-13 contrast as can be seen that with the warming temperature and solid content of the first slurry
Increase, the cohesive force of cathode membrane gradually increases, and the thickness bounce-back ratio of negative plate first reduces to be increased afterwards, lithium ion battery
Low temperature discharge ratio first increases to be reduced afterwards, and the thickness swelling of lithium ion battery at high temperature takes the lead in increasing after reducing, therefore first
The warming temperature and solid content of slurry should be moderate.From the contrast of embodiment 7 and comparative example 4 it can also be seen that when the first slurry
When material is stirred at room temperature, the performance of negative plate and lithium ion battery is poor.From the contrast of embodiment 7 and comparative example 5
In it can also be seen that when the solid content of the first slurry is too low, the performance of negative plate and lithium ion battery is also poor.This be by
In-the OH on silicon-based active material surface with can not carry out sufficient esterification containing-COOM binding agent, cause containing-
Only there is the surface of silicon-based active material in COOM binding agent, mixed when by the first slurry and the second slurry in the form of physical absorption
During conjunction, the binding agent containing-COOM can be redistributed on silicon-based active material surface, ultimately result in negative pole binding agent and exist
The distribution on the surface of silicon-based active material and carbon-based active material tends to uniform, therefore the cohesive force of cathode membrane reduces, negative pole
The thickness swelling increase of thickness the bounce-back ratio and lithium ion battery of piece at high temperature, and the low temperature performance of lithium ion battery
It is deteriorated.
Claims (10)
1. a kind of negative plate of lithium ion battery, including：
Negative current collector；And
Cathode membrane, it is arranged on negative current collector and conductive comprising negative active core-shell material, negative pole binding agent and negative pole
Agent；
Characterized in that,
Negative active core-shell material includes silicon-based active material and carbon-based active material；
The surface distributed of negative active core-shell material has negative pole binding agent；
Contain-OH in the surface of silicon-based active material；
Negative pole comprises at least the binding agent containing-COOM with binding agent, wherein, M is in H, Li, Na, K, Mg, Al, Ca, Zn
It is a kind of；
Wherein, the mass ratio of the negative pole binding agent of silicon-based active material surface distributed and silicon-based active material is more than carbon-based active
The negative pole binding agent of material surface distribution and the mass ratio of carbon-based active material.
2. the negative plate of lithium ion battery according to claim 1, it is characterised in that
Silicon-based active material is selected from the SiO that-OH silicon is contained on surface ,-OH is contained on surfacex, surface contain-OH silicon/carbon complex
In one or more, wherein, 0.6<x<1.5, surface contains carbon in-OH silicon/carbon complex and is selected from Delanium, natural
One or more in graphite, soft carbon, hard carbon, carbon fiber, carbonaceous mesophase spherules, CNT, graphene；
Carbon-based active material be selected from Delanium, native graphite, soft carbon, hard carbon, carbon fiber, carbonaceous mesophase spherules, CNT,
One or more in graphene.
3. the negative plate of lithium ion battery according to claim 1, it is characterised in that negative pole also includes butylbenzene with binding agent
One or more in rubber, polyvinyl alcohol, POLYPROPYLENE GLYCOL.
4. the negative plate of lithium ion battery according to claim 1, it is characterised in that the binding agent containing-COOM
One or more in sodium carboxymethylcellulose, polyacrylic acid, polyacrylate, sodium alginate.
5. a kind of preparation method of the negative plate of lithium ion battery, for prepare the lithium any one of claim 1-4 from
The negative plate of sub- battery, including step：
(1) silicon-based active material, the first conductive agent, the first binding agent are proportionally added into solvent deionized water and are stirred
It is even, pH value is adjusted afterwards and is less than 7, heats up afterwards and continuing stirring makes the solid content of slurry reach setting, obtain the first slurry,
Wherein ,-OH is contained on the surface of silicon-based active material, and the first binding agent comprises at least the binding agent containing-COOM, wherein, M is selected from
H, one kind in Li, Na, K, Mg, Al, Ca, Zn；
(2) carbon-based active material, the second conductive agent, the second binding agent are proportionally added into solvent deionized water and are stirred
It is even, obtain the second slurry that solid content is setting；
(3) the first slurry and the second slurry are mixed and stirred for uniformly, obtaining mixed slurry, wherein, negative active core-shell material includes
Silicon-based active material and carbon-based active material, the surface distributed of negative active core-shell material have negative pole binding agent, and negative pole bonds
Agent includes the first binding agent and the second binding agent, and negative pole includes the first conductive agent and the second conductive agent, silicon-based active with conductive agent
The negative pole binding agent of material surface distribution and the mass ratio of silicon-based active material are more than the negative of carbon-based active material surface distributed
The mass ratio of pole binding agent and carbon-based active material；
(4) mixed slurry is obtained into the negative plate of lithium ion battery coated on negative current collector after drying.
6. the preparation method of the negative plate of lithium ion battery according to claim 5, it is characterised in that in step (1),
The mass ratio of the binding agent containing-COOM and silicon-based active material in first binding agent is (1:99)~(10:90).
7. the preparation method of the negative plate of lithium ion battery according to claim 5, it is characterised in that in step (1),
First binding agent also includes the one or more in butadiene-styrene rubber, polyvinyl alcohol, POLYPROPYLENE GLYCOL.
8. the preparation method of the negative plate of lithium ion battery according to claim 5, it is characterised in that in step (2),
Second binding agent includes the one or more in the binding agent containing-COOM, butadiene-styrene rubber, polyvinyl alcohol, POLYPROPYLENE GLYCOL.
9. the preparation method of the negative plate of lithium ion battery according to claim 8, it is characterised in that in step (2),
The mass ratio of the binding agent containing-COOM and carbon-based active material in second binding agent is (0:100)~(5:95).
10. a kind of lithium ion battery, including：
Positive plate；
Negative plate；
Barrier film, it is interval between positive plate and negative plate；And
Electrolyte；
Characterized in that,
The negative plate is the negative plate of the lithium ion battery according to any one of claim 1-4.
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Cited By (1)
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|---|---|---|---|---|
| KR102328257B1 (en) * | 2017-12-27 | 2021-11-18 | 주식회사 엘지에너지솔루션 | Binder for lithium-sulfur battery, positive electrode and lithium-sulfur battery comprising the same |
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| CN113839009B (en) * | 2021-08-23 | 2023-01-31 | 惠州锂威新能源科技有限公司 | Negative electrode slurry and preparation method thereof, negative electrode plate and secondary battery |
| CN113764625B (en) * | 2021-08-26 | 2023-07-14 | 蜂巢能源科技有限公司 | Sulfide silicon-based negative plate, preparation method thereof and all-solid-state lithium ion battery |
| CN114335521A (en) * | 2021-11-22 | 2022-04-12 | 惠州市豪鹏科技有限公司 | Negative plate material, negative plate, battery preparation method and battery |
| CN117293314B (en) * | 2023-09-25 | 2024-04-12 | 浙江煌能新能源科技有限公司 | Adhesive for improving electrical property of silicon-based negative electrode, battery negative electrode and application |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101350404A (en) * | 2008-09-04 | 2009-01-21 | 上海交通大学 | Lithium ion battery cathode and preparation method thereof |
| CN101969114A (en) * | 2010-09-26 | 2011-02-09 | 东莞新能源科技有限公司 | Lithium-ion secondary battery and preparation method for pole piece thereof |
| CN103887507A (en) * | 2012-12-19 | 2014-06-25 | 三星Sdi株式会社 | Negative electrode for rechargeable lithium battery, method of preparing the same and rechargeable lithium battery including the same |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101093698B1 (en) * | 2010-01-05 | 2011-12-19 | 삼성에스디아이 주식회사 | Negative electrode for rechargeable lithium battery and rechargeable lithium battery including same |
-
2014
- 2014-07-10 CN CN201410326711.8A patent/CN105304858B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101350404A (en) * | 2008-09-04 | 2009-01-21 | 上海交通大学 | Lithium ion battery cathode and preparation method thereof |
| CN101969114A (en) * | 2010-09-26 | 2011-02-09 | 东莞新能源科技有限公司 | Lithium-ion secondary battery and preparation method for pole piece thereof |
| CN103887507A (en) * | 2012-12-19 | 2014-06-25 | 三星Sdi株式会社 | Negative electrode for rechargeable lithium battery, method of preparing the same and rechargeable lithium battery including the same |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR102328257B1 (en) * | 2017-12-27 | 2021-11-18 | 주식회사 엘지에너지솔루션 | Binder for lithium-sulfur battery, positive electrode and lithium-sulfur battery comprising the same |
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