CN110492066A - A kind of anode plate for lithium ionic cell of quick charge and preparation method thereof - Google Patents
A kind of anode plate for lithium ionic cell of quick charge and preparation method thereof Download PDFInfo
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- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
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- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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Abstract
The invention discloses a kind of anode plate for lithium ionic cell of quick charge of the present invention and preparation method thereof, so that lithium ion battery has 4C or more rapid charge characteristic, and temperature rise is low, and cycle performance is excellent.The anode plate for lithium ionic cell includes collector, and negative electrode slurry is coated on the collector, and the negative electrode slurry includes negative electrode active material, and the negative electrode active material is the first artificial graphite and the second artificial graphite；The partial size D50 of first artificial graphite is 6-8 μm, and the partial size D50 of second artificial graphite is 10-12 μm；The mass ratio of first artificial graphite and the second artificial graphite is (70-73): (21-25)；The coated face density of the negative electrode slurry is 160-170g/m2, the compacted density of the negative electrode slurry is 1-2g/cm3。
Description
Technical field
The present invention relates to technical field of lithium ion, negative more particularly to a kind of lithium ion battery of quick charge
Pole piece and preparation method thereof.
Background technique
With portable electronic products, the high speed development of electric car, market mentions the quick charge capability of lithium ion battery
Requirements at the higher level out.Lithium ion battery commercial at present can only generally carry out 0.5C or 0.2C charging, the charging time at 2 hours even
5 hours or more, the charging time was partially long, limited its use.With the quickening that people's life section gathers, more and more users wish
Lithium ion battery can be fully charged with the shorter time, and then the continuation of the journey anxiety of people is solved from quick charge angle.
When existing lithium ion battery progress 2C or more charges, it may appear that lithium ion is enriched in negative terminal surface, forms lithium gold
The phenomenon that category, electrode polarization is serious, charging capacity reduces, cycle life decline, while battery heat production increases when large current charge,
Temperature increases, and causes safety problem.
In order to overcome the defect of lithium ion battery quick charge, there is researcher by Development of Novel electrolyte, addition is added
The approach such as agent improve the rapid charge characteristic of lithium ion battery.However, the results showed that inevitably draw in modifying process
The reduction of other performances, such as cycle performance and security performance are played.
Therefore, how further to shorten the charging time of lithium ion battery, while guaranteeing lithium ion battery in charging process
Surface temperature rising is low, and does not influence the cycle performance of lithium ion battery, becomes urgent problem to be solved.
Summary of the invention
In order to make up the defect of prior art, the present invention provides the anode plate for lithium ionic cell and its system of a kind of quick charge
Preparation Method, so that lithium ion battery has 4C or more rapid charge characteristic, and temperature rise is low, and cycle performance is excellent.
The technical problems to be solved by the invention are achieved by the following technical programs:
A kind of anode plate for lithium ionic cell of quick charge, the anode plate for lithium ionic cell include collector, the collector
On be coated with negative electrode slurry, the negative electrode slurry includes negative electrode active material, the negative electrode active material be the first artificial graphite
With the second artificial graphite；The partial size D50 of first artificial graphite is 6-8 μm, and the partial size D50 of second artificial graphite is
10-12μm；The mass ratio of first artificial graphite and the second artificial graphite is (70-73): (21-25)；The negative electrode slurry
Coated face density be 160-170g/m2, the compacted density of the negative electrode slurry is 1-2g/cm3。
Further, the partial size D50 of first artificial graphite is 7 μm, and the partial size D50 of second artificial graphite is
11μm；The mass ratio of first artificial graphite and the second artificial graphite is 71:23；The coated face density of the negative electrode slurry is
163g/m2, the compacted density of the negative electrode slurry is 1.5g/cm3。
Further, the negative electrode slurry further includes conductive agent, thickener and binder.
Further, the negative electrode slurry includes the material of following parts by weight: 70-73 the first artificial graphite of part, 21-25
The second artificial graphite of part, 1-2 parts of conductive agents, 1-2 parts of thickeners, 3-4 parts of binders.
Further, the conductive agent is superconduction carbon black；The thickener is sodium carboxymethylcellulose；The binder is
SBR emulsion.
The present invention also provides the preparation methods of the anode plate for lithium ionic cell of above-mentioned quick charge, include the following steps:
S1. 70-75 parts of deionized waters and 1-2 parts of thickeners are added in blender, stirring is sufficiently dissolved to thickener, vacuum
Glue is made, for use in bubble removing；
S2. 70-73 the first artificial graphite of part, the second artificial graphite of 21-25 part and 1-2 parts of conductive agents are stirred evenly, is obtained
Powder；The partial size D50 of first artificial graphite is 6-8 μm, and the partial size D50 of second artificial graphite is 10-12 μm；
S3. 20% of glue gross mass obtained by step S1 is added into above-mentioned powder, stirring to powder lot dispersing is graininess
Object；
S4. 50% of glue gross mass obtained by step S1 is added into slurry made from step S3, stirs mutual to granular substance
Mutually mediate；
S5. 30% of glue gross mass obtained by step S1 is added into slurry made from step S4, stirring；
S6. plus deionized water adjusts viscosity to 2000-4500cp, is eventually adding 3-4 parts of binders, stirs, vacuum degassing bubble passes through
The sieve of 150-200 mesh, which is sieved, to discharge, and obtains negative electrode slurry；
S7. on a current collector by negative electrode slurry obtained coating, anode plate for lithium ionic cell is made after drying, roll-in；Its
In, the coated face density of the negative electrode slurry is 160-170g/m2；Compacted density is 1-2g/cm3。
Further, the revolution speed in step S1, being stirred, and being stirred using planetary stirring machine is 35rpm, when stirring
Between be 150 min；The revolution speed in step S2, being stirred, and being stirred using planetary stirring machine is 20rpm, and rotational velocity is
200rpm, mixing time 30min.
Further, in step S3, the revolution speed of stirring is 20rpm, rotational velocity 500rpm, and mixing time is
30min；In step S4, the revolution speed of stirring is 40rpm, rotational velocity 1500rpm, mixing time 120min；Step
In S5, the revolution speed of stirring is 30rpm, rotational velocity 2000rpm, mixing time 90min；In step S6, stirring
Revolution speed is 30rpm, rotational velocity 800rpm, mixing time 30min.
Further, the collector is the copper foil with a thickness of 8-12 μm；Drying temperature is 60-100 DEG C in step S7.
Further, the parameter of the vacuum degassing bubble are as follows: in the case where vacuum degree is less than -0.08 Mpa bubble removing 30 minutes.
The invention has the following beneficial effects:
In the present invention, changed by negative electrode slurry system, coated face density, the compacted density to anode plate for lithium ionic cell
Into so that the lithium ion battery using negative electrode tab of the present invention has 4C or more rapid charge characteristic, and temperature rise is low, cycle performance
It is excellent.
In the present invention, negative electrode active material in the negative electrode slurry artificial graphite different using two kinds of partial sizes, wherein and lead to
Both adjustment ratio is crossed, mix and match guarantees that small particle artificial graphite accounting is big, and big partial size artificial graphite accounting is small, so that
The artificial graphite of different-grain diameter comes into full contact with, it is ensured that there are more small gaps for negative electrode tab, improve negative electrode tab imbibition ability and lithium
The conduction velocity of ion.The impedance that battery is effectively reduced by the synergistic effect of two kinds of different-grain diameter graphite makes battery can be into
The above quick charge of row 4C, while battery temperature rise is controlled, cycle life is maintained.
The present invention improves coated face density and compacted density, and coated face density and compacted density are respectively 160-
170g/m2And 1-2g/cm3, by control coated face density and compacted density, the thickness and porosity of negative electrode tab are controlled, favorably
In reducing the impedance that lithium ion migrates between a positive electrode and a negative electrode in charge and discharge process, quick charge is helped to realize.
The present invention improves homogenization process, homogenization process include it is dry-mixed, point three steps add glue, adjust viscosity, sieving,
By mixing time in control process, mixing speed plus glue ratio, slurry viscosity, so that slurry each component is uniformly dispersed, be not easy
Reunite and settles.
Detailed description of the invention
Fig. 1 is the multiplying power charging performance test result of the battery of the negative electrode tab containing embodiment 1 in the present invention；
Fig. 2 is the cycle performance test chart of the battery of the negative electrode tab containing embodiment 1 in the present invention；
Fig. 3 is the charging performance test result of the battery containing different negative electrode tabs.
Specific embodiment
In a first aspect, the present invention provides a kind of anode plate for lithium ionic cell of quick charge, the negative electrode of lithium ion battery
Piece includes collector, and negative electrode slurry is coated on the collector, and the negative electrode slurry includes negative electrode active material, the cathode
Active material is the first artificial graphite and the second artificial graphite.
The partial size D50 of first artificial graphite is 6-8 μm, and the partial size D50 of second artificial graphite is 10-12 μ
m；It is highly preferred that the partial size D50 of first artificial graphite is 7 μm, the partial size D50 of second artificial graphite is 11 μm.
The mass ratio of first artificial graphite and the second artificial graphite is (70-73): (21-25)；It is highly preferred that described
The mass ratio of first artificial graphite and the second artificial graphite is 73:24.
The coated face density of the negative electrode slurry is 160-170g/m2, it is highly preferred that the coated face density of the negative electrode slurry is
163g/m2.Inventor has found under study for action, if the coated face density of negative electrode slurry meets the requirement of above-mentioned specific value range,
Gained lithium ion battery can have both good rapid charging performance and good cycle life energy.The coated face density of the negative electrode slurry
Greater than 170g/m2, the migration path that will lead to battery lithium ion during the charging process is elongated, and the interface impedance of battery increases, electricity
Pond polarization increases, and is unfavorable for quick charge；And the coated face density of negative electrode slurry is less than 160g/m2When, the capacity of battery is therewith
Reduce, influences its market competitiveness.
The compacted density of the negative electrode slurry is 1-2g/cm3, it is highly preferred that the compacted density of the negative electrode slurry is
1.5g/cm3.Inventor has found under study for action, if the compacted density of negative electrode slurry meets the requirement of above-mentioned specific value range, institute
Good rapid charging performance and good cycle life energy can be had both by obtaining lithium ion battery.When compacted density is less than 1g/cm3, can lead
Negative electrode tab demoulding picking is caused, electronic conductance is poor and generate analysis lithium when charging, influences the rapid charging performance of battery；Compacted density mistake
Greatly, cause the contact in negative electrode slurry between each component too close, electrolyte infiltration is difficult, and charging performance is deteriorated.
In the present invention, the negative electrode slurry further includes conductive agent, thickener and binder.
Specifically, the negative electrode slurry includes the material of following parts by weight: 70-73 the first artificial graphite of part, 21-25
The second artificial graphite of part, 1-2 parts of conductive agents, 1-2 parts of thickeners, 3-4 parts of binders.
Suitable conductive agent is conducive to the conduction of lithium ion, reduces the resistance of negative electrode tab.The conductive agent is preferably superconduction
Carbon black, conductive agent of the invention include but is not limited to material enumerated supra, and it is unlisted in the present invention to be also possible to other
But by other materials well-known to those skilled in the art, such as can also be that graphene, electrically conductive graphite, carbon fiber, carbon are received
One of mitron is a variety of.
The thickener is preferably sodium carboxymethylcellulose, and thickener of the invention includes but is not limited to enumerated supra
Material, be also possible to other it is unlisted in the present invention but by other materials well-known to those skilled in the art.
Binder can increase the bonding between cohesive force, negative electrode slurry and collector in negative electrode slurry between particle
Power keeps good caking property in charge and discharge negative electrode volume change procedure, avoids cathode powder and falls off, ensure that cathode
The integrality of chip architecture helps to improve the cycle life of battery.In the present invention, the binder is SBR emulsion, this
The binder of invention includes but is not limited to material enumerated supra, be also possible to other it is unlisted in the present invention but by this
Other materials known to the technical staff of field, such as can also be acroleic acid binding agent.
In the present invention, carried out by negative electrode slurry system, coated face density, the compacted density to anode plate for lithium ionic cell
It improves, so that the lithium ion battery using negative electrode tab of the present invention has 4C or more rapid charge characteristic, and temperature rise is low, cyclicity
It can be excellent.
In the present invention, the negative electrode slurry system of anode plate for lithium ionic cell, coated face density, compacted density these three parameters
Be it is interrelated, inseparable, the fast charge and cycle performance of three's joint effect lithium ion battery meet following conditions: negative
Pole active material is the first artificial graphite and the second artificial graphite；The partial size D50 of first artificial graphite is 6-8 μm, described
The partial size D50 of second artificial graphite is 10-12 μm；The mass ratio of first artificial graphite and the second artificial graphite is (70-
73): (21-25)；The coated face density of the negative electrode slurry is 160-170g/m2, the compacted density of the negative electrode slurry is 1-
2g/cm3Battery fast charge ability can be improved, while battery also has both good service life cycle；Its technical effect is not
It is that these three parameters are simply superimposed, is embodied in quick charge capability and long circulation life is greatly improved, realize " 1+
The technical effect of 1+1 > 3 " achieves unexpected technical effect.
A kind of artificial graphite is generally only used in the prior art as negative electrode active material, the lithium ion battery of this system
General impedance is big, Wen Shenggao when quick charge, and cycle life is low.Inventor is had found by numerous studies, using different-grain diameter
Artificial graphite has a degree of influence to the cycle performance of battery and fast charge ability as negative electrode active material.The present invention
In, the artificial graphite that the negative electrode active material in negative electrode slurry uses two kinds of partial sizes different, and by adjusting the two ratio, mixing
Collocation guarantees that small particle artificial graphite accounting is big, and big partial size artificial graphite accounting is small, so that the artificial graphite of different-grain diameter fills
Tap touching, it is ensured that there are more small gaps for negative electrode tab, improve the conduction velocity of negative electrode tab imbibition ability and lithium ion.Pass through two
The synergistic effect of kind different-grain diameter graphite effectively reduces the impedance of battery, makes battery that can carry out 4C or more quick charge, simultaneously
Control battery temperature rise, cycle life is maintained.
The present invention improves coated face density and compacted density, and coated face density and compacted density are respectively 160-
170g/m2And 1.5g/cm3, by control coated face density and compacted density, the thickness and porosity of negative electrode tab are controlled, favorably
In the impedance for reducing lithium ion battery, quick charge is helped to realize.
Second aspect, the present invention also provides the preparation methods of the anode plate for lithium ionic cell of above-mentioned quick charge, including such as
Lower step:
S1. 70-75 parts of deionized waters and 1-2 parts of thickeners are added in blender, stirring is sufficiently dissolved to thickener, vacuum
Glue is made, for use in bubble removing；
S2. 70-73 the first artificial graphite of part, the second artificial graphite of 21-25 part and 1-2 parts of conductive agents are stirred evenly, is obtained
Powder；
S3. 20% of glue gross mass obtained by step S1 is added into above-mentioned powder, stirring to powder lot dispersing is graininess
Object；
S4. 50% of glue gross mass obtained by step S1 is added into slurry made from step S3, stirs mutual to granular substance
Mutually mediate；
S5. 30% of glue gross mass obtained by step S1 is added into slurry made from step S4, stirring；
S6. plus deionized water adjusts viscosity to 2000-4500cp, is eventually adding 3-4 parts of binders, stirs, vacuum degassing bubble passes through
The sieve of 150-200 mesh, which is sieved, to discharge, and obtains negative electrode slurry；
S7. on a current collector by negative electrode slurry obtained coating, anode plate for lithium ionic cell is made after drying, roll-in；Its
In, the coated face density of the negative electrode slurry is 160-170g/m2；Compacted density is 1-2g/cm3。
Wherein, the revolution speed in step S1, being stirred, and being stirred using planetary stirring machine is 35rpm, and mixing time is
150 min；The revolution speed in step S2, being stirred, and being stirred using planetary stirring machine is 20rpm, and rotational velocity is
200rpm, mixing time 30min；In step S3, the revolution speed of stirring is 20rpm, rotational velocity 500rpm, when stirring
Between be 30min；In step S4, the revolution speed of stirring is 40rpm, rotational velocity 1500rpm, mixing time 120min；
In step S5, the revolution speed of stirring is 30rpm, rotational velocity 2000rpm, mixing time 90min；In step S6, stir
The revolution speed mixed is 30rpm, rotational velocity 800rpm, mixing time 30min.
Deionized water purity is high, impurity is few, can make to be dissolved in negative electrode active material, binder and conductive agent therein not
It easily chemically reacts, manufactured battery side reaction is few, and performance is stablized.
In the present invention, the collector is preferably copper foil, but not limited to this, collector of the invention is also possible to other
It is unlisted in the present invention but by other materials well-known to those skilled in the art.The selection of copper thickness, comprehensive consideration
The factors such as conductive capability, heat production/heat-sinking capability, tensile strength, the battery lightweight of copper foil, and the thickness of copper foil is preferably 8-12
μm。
Drying temperature is 60-100 DEG C in step S7, such as can be 60 DEG C, 70 DEG C, 80 DEG C, 90 DEG C, 100 DEG C.
The parameter of the vacuum degassing bubble is preferred are as follows: in the case where vacuum degree is less than -0.08 Mpa bubble removing 30 minutes.
The prior art generally comprises a dry-mixed, step or two steps add glue, adjust viscosity, sieving, the slurry of this technology preparation
Each component dispersion is uneven, is easy to reunite, settle.The present invention improves homogenization process, homogenization process include it is dry-mixed, points three
Step plus glue adjust viscosity, sieving, by mixing time in control process, mixing speed plus glue ratio, slurry viscosity, make
Slurry each component is uniformly dispersed, not easy to reunite and sedimentation.
The present invention will now be described in detail with reference to examples, and the examples are only preferred embodiments of the present invention,
It is not limitation of the invention.
Embodiment 1
A kind of anode plate for lithium ionic cell of quick charge, preparation method include the following steps:
S1. 72 parts of deionized waters and 1.5 parts of thickeners are added in the planetary stirring machine that volume is 60L, with revolution speed
35rpm, 150 min of stirring are sufficiently dissolved to thickener, and in the case where vacuum degree is less than -0.08 Mpa bubble removing 30 minutes, glue is made
Liquid, for use；
S2. 71 part of first artificial graphite, 23 part of second artificial graphite and 1.6 parts of conductive agents are added to the row that volume is 60L
In planetary blender, with revolution speed 20rpm, rotational velocity 200rpm, 30min is stirred, uniformly mixed powder is obtained；Its
In, the partial size D50 of first artificial graphite is 7 μm, and the partial size D50 of second artificial graphite is 11 μm；
S3. it is added 20% of glue gross mass obtained by step S1, into above-mentioned powder with revolution speed 20rpm, rotational velocity
500rpm, stirring 30min to powder lot dispersing are granular substance；
S4. 50% of glue gross mass obtained by step S1 is added into slurry made from step S3, with revolution speed 40rpm,
Rotational velocity 1500rpm, stirring 120min are mediated mutually to granular substance；
S5. 30% of glue gross mass obtained by step S1 is added into slurry made from step S4, with revolution speed 30rpm,
Rotational velocity 2000rpm, 90min is to being uniformly dispersed for stirring；
S6. deionized water is added and adjusts viscosity to 2500cp, 3.6 parts of binders are eventually adding, with revolution speed 30rpm, rotation
Speed 800rpm stirs 30min, and in the case where vacuum degree is less than -0.08 Mpa bubble removing 30 minutes, the sieve through 200 mesh, which is crossed, to be sifted out
Material, obtains negative electrode slurry；
S7. negative electrode slurry obtained is coated on the copper foil with a thickness of 8 μm, it is negative that lithium ion battery is made after drying, roll-in
Pole piece；Wherein, the coated face density of the negative electrode slurry is 163g/m2；Compacted density is 1.5g/cm3；Drying temperature is 60-
100℃。
The conductive agent is superconduction carbon black；The thickener is sodium carboxymethylcellulose；The binder is butadiene-styrene rubber
Lotion.
Embodiment 2
A kind of anode plate for lithium ionic cell of quick charge, preparation method include the following steps:
S1. 70 parts of deionized waters and 1 part of thickener are added in the planetary stirring machine that volume is 60L, with revolution speed
35rpm, 150 min of stirring are sufficiently dissolved to thickener, and in the case where vacuum degree is less than -0.08 Mpa bubble removing 30 minutes, glue is made
Liquid, for use；
S2. 70 part of first artificial graphite, 21 part of second artificial graphite and 1 part of conductive agent are added to the planet that volume is 60L
In formula blender, with revolution speed 20rpm, rotational velocity 200rpm, 30min is stirred, uniformly mixed powder is obtained；Wherein,
The partial size D50 of first artificial graphite is 6 μm, and the partial size D50 of second artificial graphite is 10 μm；
S3. it is added 20% of glue gross mass obtained by step S1, into above-mentioned powder with revolution speed 20rpm, rotational velocity
500rpm, stirring 30min to powder lot dispersing are granular substance；
S4. 50% of glue gross mass obtained by step S1 is added into slurry made from step S3, with revolution speed 40rpm,
Rotational velocity 1500rpm, stirring 120min are mediated mutually to granular substance；
S5. 30% of glue gross mass obtained by step S1 is added into slurry made from step S4, with revolution speed 30rpm,
Rotational velocity 2000rpm, 90min is to being uniformly dispersed for stirring；
S6. deionized water is added and adjusts viscosity to 2000cp, 3 parts of binders are eventually adding, with revolution speed 30rpm, from revolving speed
800rpm is spent, 30min is stirred, in the case where vacuum degree is less than -0.08 Mpa bubble removing 30 minutes, the sieve through 150 mesh, which is sieved, to discharge,
Obtain negative electrode slurry；
S7. negative electrode slurry obtained is coated on the copper foil with a thickness of 12 μm, lithium ion battery is made after drying, roll-in
Negative electrode tab；Wherein, the coated face density of the negative electrode slurry is 160g/m2；Compacted density is 1g/cm3；Drying temperature is 60-
100℃。
The conductive agent is superconduction carbon black；The thickener is sodium carboxymethylcellulose；The binder is butadiene-styrene rubber
Lotion.
Embodiment 3
A kind of anode plate for lithium ionic cell of quick charge, preparation method include the following steps:
S1. 75 parts of deionized waters and 2 parts of thickeners are added in the planetary stirring machine that volume is 60L, with revolution speed
35rpm, 150 min of stirring are sufficiently dissolved to thickener, and in the case where vacuum degree is less than -0.08 Mpa bubble removing 30 minutes, glue is made
Liquid, for use；
S2. 73 part of first artificial graphite, 25 part of second artificial graphite and 2 parts of conductive agents are added to the planet that volume is 60L
In formula blender, with revolution speed 20rpm, rotational velocity 200rpm, 30min is stirred, uniformly mixed powder is obtained；Wherein,
The partial size D50 of first artificial graphite is 8 μm, and the partial size D50 of second artificial graphite is 12 μm；
S3. it is added 20% of glue gross mass obtained by step S1, into above-mentioned powder with revolution speed 20rpm, rotational velocity
500rpm, stirring 30min to powder lot dispersing are granular substance；
S4. 50% of glue gross mass obtained by step S1 is added into slurry made from step S3, with revolution speed 40rpm,
Rotational velocity 1500rpm, stirring 120min are mediated mutually to granular substance；
S5. 30% of glue gross mass obtained by step S1 is added into slurry made from step S4, with revolution speed 30rpm,
Rotational velocity 2000rpm, 90min is to being uniformly dispersed for stirring；
S6. deionized water is added and adjusts viscosity to 4500cp, 4 parts of binders are eventually adding, with revolution speed 30rpm, from revolving speed
800rpm is spent, 30min is stirred, in the case where vacuum degree is less than -0.08 Mpa bubble removing 30 minutes, the sieve through 200 mesh, which is sieved, to discharge,
Obtain negative electrode slurry；
S7. negative electrode slurry obtained is coated on the copper foil with a thickness of 8-12 μm, lithium-ion electric is made after drying, roll-in
Pond negative electrode tab；Wherein, the coated face density of the negative electrode slurry is 170g/m2；Compacted density is 2g/cm3；Drying temperature is 60-
100℃。
The conductive agent is superconduction carbon black；The thickener is sodium carboxymethylcellulose；The binder is butadiene-styrene rubber
Lotion.
Embodiment 4
A kind of anode plate for lithium ionic cell of quick charge, preparation method include the following steps:
S1. 74 parts of deionized waters and 1 part of thickener are added in the planetary stirring machine that volume is 60L, with revolution speed
35rpm, 150 min of stirring are sufficiently dissolved to thickener, and in the case where vacuum degree is less than -0.08 Mpa bubble removing 30 minutes, glue is made
Liquid, for use；
S2. 70 part of first artificial graphite, 25 part of second artificial graphite and 1 part of conductive agent are added to the planet that volume is 60L
In formula blender, with revolution speed 20rpm, rotational velocity 200rpm, 30min is stirred, uniformly mixed powder is obtained；Wherein,
The partial size D50 of first artificial graphite is 7 μm, and the partial size D50 of second artificial graphite is 12 μm；
S3. it is added 20% of glue gross mass obtained by step S1, into above-mentioned powder with revolution speed 20rpm, rotational velocity
500rpm, stirring 30min to powder lot dispersing are granular substance；
S4. 50% of glue gross mass obtained by step S1 is added into slurry made from step S3, with revolution speed 40rpm,
Rotational velocity 1500rpm, stirring 120min are mediated mutually to granular substance；
S5. 30% of glue gross mass obtained by step S1 is added into slurry made from step S4, with revolution speed 30rpm,
Rotational velocity 2000rpm, 90min is to being uniformly dispersed for stirring；
S6. deionized water is added and adjusts viscosity to 2000-4500cp, is eventually adding 4 parts of binders, with revolution speed 30rpm, certainly
Rotary speed 800rpm stirs 30min, in the case where vacuum degree is less than -0.08 Mpa bubble removing 30 minutes, the sieve through 150-200 mesh
Sieving discharging, obtains negative electrode slurry；
S7. negative electrode slurry obtained is coated on the copper foil with a thickness of 10 μm, lithium ion battery is made after drying, roll-in
Negative electrode tab；Wherein, the coated face density of the negative electrode slurry is 160g/m2；Compacted density is 1.5g/cm3；Drying temperature is 60-
100℃。
The conductive agent is superconduction carbon black；The thickener is sodium carboxymethylcellulose；The binder is butadiene-styrene rubber
Lotion.
Comparative example 1
It based on embodiment 1, the difference is that only: step S2 in this comparative example 1 are as follows: by 94 part of first artificial graphite and 1.6 parts
Conductive agent is added in the planetary stirring machine that volume is 60L, with revolution speed 20rpm, rotational velocity 200rpm, stirring
30min obtains uniformly mixed powder；Wherein, the partial size D50 of first artificial graphite is 7 μm.
Comparative example 2
It based on embodiment 1, the difference is that only: step S2 in this comparative example 2 are as follows: by 94 part of second artificial graphite and 1.6 parts
Conductive agent is added in the planetary stirring machine that volume is 60L, with revolution speed 20rpm, rotational velocity 200rpm, stirring
30min obtains uniformly mixed powder；Wherein, the partial size D50 of second artificial graphite is 11 μm.
Comparative example 3
Based on embodiment 1, the difference is that only: the coated face density of negative electrode slurry described in this comparative example 3 is 200g/m2。
Comparative example 4
Based on embodiment 1, the difference is that only: the coated face density of negative electrode slurry described in this comparative example 4 is 150g/m2。
Comparative example 5
Based on embodiment 1, the difference is that only: compacted density is 0.8g/cm in this comparative example 53。
Comparative example 6
Based on embodiment 1, the difference is that only: compacted density is 3g/cm in this comparative example 63。
Comparative example 7
A kind of anode plate for lithium ionic cell of quick charge, preparation method include the following steps:
S1. 72 parts of deionized waters and 1.5 parts of thickeners are added in the planetary stirring machine that volume is 60L, with revolution speed
35rpm, 150 min of stirring are sufficiently dissolved to thickener, and in the case where vacuum degree is less than -0.08 Mpa bubble removing 30 minutes, glue is made
Liquid, for use；
S2. 71 part of first artificial graphite, 23 part of second artificial graphite and 1.6 parts of conductive agents are added to the row that volume is 60L
In planetary blender, with revolution speed 20rpm, rotational velocity 200rpm, 30min is stirred, uniformly mixed powder is obtained；Its
In, the partial size D50 of first artificial graphite is 7 μm, and the partial size D50 of second artificial graphite is 11 μm；
S3. glue obtained by Overall Steps S1 is added, into above-mentioned powder with revolution speed 30rpm, rotational velocity
2000rpm, 240min is to being uniformly dispersed for stirring；
S4. deionized water is added and adjusts viscosity to 2500cp, 3.6 parts of binders are eventually adding, with revolution speed 30rpm, rotation
Speed 800rpm stirs 30min, and in the case where vacuum degree is less than -0.08 Mpa bubble removing 30 minutes, the sieve through 200 mesh, which is crossed, to be sifted out
Material, obtains negative electrode slurry；
S7. negative electrode slurry obtained is coated on the copper foil with a thickness of 8 μm, it is negative that lithium ion battery is made after drying, roll-in
Pole piece；Wherein, the coated face density of the negative electrode slurry is 163g/m2；Compacted density is 1.5g/cm3；Drying temperature is 60-
100℃。
The conductive agent is superconduction carbon black；The thickener is sodium carboxymethylcellulose；The binder is butadiene-styrene rubber
Lotion.
Test example
Anode plate for lithium ionic cell made from above-described embodiment 1 and comparative example 1-7 is cut according to identical length and width standard,
And core is made by winding with conventional positive plate, diaphragm, it is assembled into the battery of same model, injects identical electrolyte,
After the chemical conversion of identical chemical synthesis technology, performance test and normal temperature circulation test are charged the battery, test result is referring to Fig. 1-
3。
Wherein, charging performance test condition in Fig. 1 are as follows: battery surface temperature, the electricity that SOC is 30% are detected with thermistor
Pond is shelved 10 minutes at 25 DEG C, with 1C electric current constant-current discharge to 2.8V, is shelved 60 minutes, is restored to 25 to battery surface temperature
DEG C, with 1C electric current constant-current constant-voltage charging to blanking voltage 4.2V, cut-off current 0.05C；It shelves after ten minutes, with 1C electric current constant current
It is discharged to 2.8V, is then shelved 60 minutes, after battery surface temperature is restored to 25 DEG C, then extremely with 3C electric current constant-current constant-voltage charging
4.2V, cut-off current 0.05C；It shelves after ten minutes, with 1C electric current constant-current discharge to 2.8V, then shelves 60 minutes, to battery
After surface temperature returns to 25 DEG C, then with 5C electric current constant-current constant-voltage charging to 4.2V, cut-off current 0.05C；Shelve after ten minutes, with
Then 1C electric current constant-current discharge is shelved 60 minutes, is filled after battery temperature returns to 25 DEG C, then with 8C electric current constant current constant voltage to 2.8V
Electricity is to 4.2V, cut-off current 0.05C；So far multiplying power test is completed, and temperature rise is maximum temperature and 25 in each multiplying power charging process
DEG C difference.
Charging performance test condition in Fig. 3 are as follows:
5C, 4.2V constant-current charge volume percent (%): refer to battery during 5C electric current constant-current constant-voltage charging, in constant-current phase
The capacity being filled with accounts for the percentage of entire constant-current constant-voltage charging stage total capacity, calculating formula Cap.CC/Cap.CCCV；
5C, 4.2V constant-current constant-voltage charging temperature rise (DEG C): refer to battery during 5C electric current constant-current constant-voltage charging, the highest temperature of battery
Degree and 25 DEG C of difference, calculating formula Tmax-25℃；
Capacity retention ratio (%) after 4C/-1C, 4.2V/2.8V are recycled 500 times: refer to battery with 4C constant-current constant-voltage charging to 4.2V,
0.05C, then with 1C constant-current discharge to 2.8V, in this way charge and discharge cycles 500 times, the 500th discharge capacity and nominal appearance
Measure the ratio of (cyclic discharge capacity for the first time), calculating formula Cap.discharge(500th)/Cap.discharge (1st).
From it is found that the battery using negative electrode tab in embodiment 1 can carry out 4C or more quick charge, while making electricity in Fig. 1-2
Pond temperature rise is controlled, and cycle life is maintained.
As can be seen from Figure 3, in the present invention, negative electrode slurry system, coated face density, the compacted density of anode plate for lithium ionic cell
These three parameters are interrelated, inseparable, the fast charge and cycle performance of three's joint effect lithium ion battery, under satisfaction
State condition: negative electrode active material is the first artificial graphite and the second artificial graphite；The partial size D50 of first artificial graphite is
6-8 μm, the partial size D50 of second artificial graphite is 10-12 μm；The matter of first artificial graphite and the second artificial graphite
Amount is than being (70-73): (21-25)；The coated face density of the negative electrode slurry is 160-170g/m2, the pressure of the negative electrode slurry
Real density is 1-2g/cm3Battery fast charge ability can be improved, while battery also has both good service life cycle；Its skill
Art effect is not that these three parameters are simply superimposed, and is embodied in quick charge capability and long circulation life obtains very big mention
Height realizes the technical effect of " 1+1+1 > 3 ", achieves unexpected technical effect.Lack any in these three parameters
One, battery cannot have both good fast charge ability, good cycle performance and low temperature rise.
Embodiments of the present invention above described embodiment only expresses, the description thereof is more specific and detailed, but can not
Therefore limitations on the scope of the patent of the present invention are interpreted as, as long as skill obtained in the form of equivalent substitutions or equivalent transformations
Art scheme should all be fallen within the scope and spirit of the invention.
Claims (10)
1. a kind of anode plate for lithium ionic cell of quick charge, the anode plate for lithium ionic cell include collector, the afflux
Negative electrode slurry is coated on body, the negative electrode slurry includes negative electrode active material；It is characterized in that, the negative electrode active material is
First artificial graphite and the second artificial graphite；The partial size D50 of first artificial graphite is 6-8 μm, second artificial graphite
Partial size D50 be 10-12 μm；The mass ratio of first artificial graphite and the second artificial graphite is (70-73): (21-25)；
The coated face density of the negative electrode slurry is 160-170g/m2, the compacted density of the negative electrode slurry is 1-2g/cm3。
2. the anode plate for lithium ionic cell of quick charge as described in claim 1, which is characterized in that first artificial graphite
Partial size D50 be 7 μm, the partial size D50 of second artificial graphite is 11 μm；First artificial graphite and the second artificial stone
The mass ratio of ink is 71:23；The coated face density of the negative electrode slurry is 163g/m2, the compacted density of the negative electrode slurry is
1.5g/cm3。
3. the anode plate for lithium ionic cell of quick charge as described in claim 1, which is characterized in that the negative electrode slurry also wraps
Include conductive agent, thickener and binder.
4. the anode plate for lithium ionic cell of quick charge as claimed in claim 3, which is characterized in that the negative electrode slurry includes
The material of following parts by weight: 70-73 the first artificial graphite of part, 21-25 the second artificial graphite of part, 1-2 parts of conductive agents, 1-2 parts
Thickener, 3-4 parts of binders.
5. the anode plate for lithium ionic cell of quick charge as claimed in claim 4, which is characterized in that the conductive agent is superconduction
Carbon black；The thickener is sodium carboxymethylcellulose；The binder is SBR emulsion.
6. a kind of preparation method of the anode plate for lithium ionic cell of quick charge, includes the following steps:
S1. 70-75 parts of deionized waters and 1-2 parts of thickeners are added in blender, stirring is sufficiently dissolved to thickener, vacuum
Glue is made, for use in bubble removing；
S2. 70-73 the first artificial graphite of part, the second artificial graphite of 21-25 part and 1-2 parts of conductive agents are stirred evenly, is obtained
Powder；The partial size D50 of first artificial graphite is 6-8 μm, and the partial size D50 of second artificial graphite is 10-12 μm；
S3. 20% of glue gross mass obtained by step S1 is added into above-mentioned powder, stirring to powder lot dispersing is graininess
Object；
S4. 50% of glue gross mass obtained by step S1 is added into slurry made from step S3, stirs mutual to granular substance
Mutually mediate；
S5. 30% of glue gross mass obtained by step S1 is added into slurry made from step S4, stirring；
S6. plus deionized water adjusts viscosity to 2000-4500cp, is eventually adding 3-4 parts of binders, stirs, vacuum degassing bubble passes through
The sieve of 150-200 mesh, which is sieved, to discharge, and obtains negative electrode slurry；
S7. on a current collector by negative electrode slurry obtained coating, anode plate for lithium ionic cell is made after drying, roll-in；Its
In, the coated face density of the negative electrode slurry is 160-170g/m2；Compacted density is 1-2g/cm3。
7. the preparation method of the anode plate for lithium ionic cell of quick charge as claimed in claim 6, which is characterized in that step S1
In, the revolution speed for being stirred, and being stirred using planetary stirring machine is 35rpm, and mixing time is 150 min；In step S2, make
The revolution speed for being stirred, and being stirred with planetary stirring machine is 20rpm, rotational velocity 200rpm, mixing time 30min.
8. the preparation method of the anode plate for lithium ionic cell of quick charge as claimed in claim 6, which is characterized in that step S3
In, the revolution speed of stirring is 20rpm, rotational velocity 500rpm, mixing time 30min；In step S4, the revolution of stirring
Speed is 40rpm, rotational velocity 1500rpm, mixing time 120min；In step S5, the revolution speed of stirring is
30rpm, rotational velocity 2000rpm, mixing time 90min；In step S6, the revolution speed of stirring is 30rpm, from revolving speed
Degree is 800rpm, mixing time 30min.
9. the preparation method of the anode plate for lithium ionic cell of quick charge as claimed in claim 6, which is characterized in that the collection
Fluid is the copper foil with a thickness of 8-12 μm；Drying temperature is 60-100 DEG C in step S7.
10. the preparation method of the anode plate for lithium ionic cell of quick charge as claimed in claim 6, which is characterized in that described
The parameter of vacuum degassing bubble are as follows: in the case where vacuum degree is less than -0.08 Mpa bubble removing 30 minutes.
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| CN111370670A (en) * | 2020-03-19 | 2020-07-03 | 陆晨杰 | Mixing method of negative electrode slurry |
| CN111584825A (en) * | 2020-06-01 | 2020-08-25 | 湖北亿纬动力有限公司 | Negative plate and preparation method and application thereof |
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