CN106252598A - A kind of high power capacity, high security lithium ion battery cathode composite pole piece and preparation method thereof, lithium ion battery - Google Patents
A kind of high power capacity, high security lithium ion battery cathode composite pole piece and preparation method thereof, lithium ion battery Download PDFInfo
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- CN106252598A CN106252598A CN201610754676.9A CN201610754676A CN106252598A CN 106252598 A CN106252598 A CN 106252598A CN 201610754676 A CN201610754676 A CN 201610754676A CN 106252598 A CN106252598 A CN 106252598A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/134—Electrodes based on metals, Si or alloys
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- 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 invention discloses a kind of high power capacity, high security lithium ion battery cathode composite pole piece and preparation method thereof, lithium ion battery.This negative pole composite pole piece includes collector, silicon layer and active material layer, on the surface of collector along the direction away from collector, is sequentially provided with silicon layer, active material layer and lithium metaaluminate composite bed.The high power capacity of the present invention, high security lithium ion battery cathode composite pole piece, arrange lithium metaaluminate composite bed on active material layer, and wherein, lithium metaaluminate has good ionic conductivity, it is possible to shortens the charging interval, improves the multiplying power charging performance of lithium ion battery；And the Li dendrite that under high rate charge-discharge, the accumulation of cathode pole piece lithium ion causes can be prevented, improve its security performance；The internal resistance of lithium ion battery can also be reduced.
Description
Technical field
The present invention relates to field of lithium ion battery, be specifically related to a kind of high power capacity, high security lithium ion battery cathode again
Close pole piece and preparation method thereof, also relate to a kind of lithium ion battery.
Background technology
Negative material is the key component of composition lithium ion battery, and negative material used in the market is main
Based on graphite type material, but graphite negative electrodes material exists that gram volume is low, high rate performance is poor, poor performance at low temperatures and safety thereof
The defects such as poor performance, therefore for meeting to high-energy-density densitybattery demand on market, need to develop a kind of gram volume high, again
The negative material that rate excellent performance, security performance are good seems the most necessary.And silica-base material, tin-based material, metal oxide materials
And lithium titanate material is expected to become negative material of future generation with its respective advantage, but although silica-base material gram volume is high,
But expansion rate is high, high rate performance difference limits it and promotes adaptation, although lithium titanate battery high rate performance and security performance are good, but
Gram volume is low and voltage platform high, causes its energy density on the low side, therefore can utilize the characteristic that the gram volume of silica-base material is high
Characteristic good with lithium titanate high rate performance, that security performance is excellent, develops a kind of excellent combination property, energy density height, multiplying power
The lithium titanate battery that excellent performance, security performance are good, and it is applied to fill soon field of lithium ion battery.
In prior art, CN104347842A discloses a kind of lithium rechargeable battery composite negative plate, including metal collection
Fluid and be deposited on the first negative electrode active layer on described metal collector surface, and coating is arranged on described first negative electrode active
The second negative electrode active layer on layer surface, described first negative electrode active layer is silicon-based active material layer, described silicon-based active material layer
Thickness be 5nm～2 μm, the material of described second negative electrode active layer includes negative active core-shell material, binding agent and conductive agent, described
Negative active core-shell material is at least one in carbon element class negative material and lithium titanate.And further disclose described silicon-based active
Material one in elementary silicon, Si oxide and silicon alloy.This composite negative plate, due to the silicon-based active material of relatively small thickness
Expect to contact with the direct of electrolyte, the volumetric expansion of buffering silicon-based active material, thus effectively solve silicon-based active material because of body
The problem amassing bulking effect and easily come off from collector, extends the service life cycle of lithium rechargeable battery；Additionally, due to it is multiple
Close negative plate and there are double storage lithium layer structures of silicon-based active material layer and the second negative electrode active layer, it is thus possible to be effectively improved negative plate
Capacity.Meanwhile, after nanorize, the conductive capability of material can be greatly improved, and therefore the entirety of collector is led by silicon-based active material
Electrical characteristics have little to no effect.Consume more lithium ion owing to silicon layer and active material layer form SEI, cause charge and discharge process
The supply of middle lithium ion is not enough, causes the lithium ion battery high rate performance deviation under the conditions of big multiplying power.
Summary of the invention
It is an object of the invention to provide a kind of high power capacity, high security lithium ion battery cathode composite pole piece, it is possible to solve
Under the conditions of big multiplying power, the problem of lithium ion battery high rate performance difference.
The present invention also aims to provide a kind of high power capacity, the preparation of high security lithium ion battery cathode composite pole piece
Method and a kind of lithium ion battery.
In order to realize object above, the high power capacity of the present invention, high security lithium ion battery cathode composite pole piece are used
Technical scheme be:
A kind of high power capacity, high security lithium ion battery cathode composite pole piece, including collector, silicon layer and active substance
Layer, on the surface of collector along the direction away from described collector, is sequentially provided with silicon layer, active material layer and lithium metaaluminate compound
Layer.
The high power capacity of the present invention, high security lithium ion battery cathode composite pole piece, arrange inclined aluminum on active material layer
Acid lithium composite bed, wherein lithium metaaluminate has good ionic conductivity, it is possible to shorten the charging interval, improves lithium ion battery
Multiplying power charging performance；And it is prevented from the Li dendrite that under high rate charge-discharge, the accumulation of cathode pole piece lithium ion causes, improves
Its security performance；The internal resistance of lithium ion battery can also be reduced.
The thickness of described silicon layer, active material layer and lithium metaaluminate composite bed is than for (4～6): (100～300): (5～
10)。
Described collector is Copper Foil or copper mesh.The thickness of collector is 8～20 μm.
The composition of described silicon layer is elementary silicon.
The active substance of described active material layer is lithium titanate.Active material layer is by lithium titanate, binding agent A and conductive agent A
Composition.The mass ratio of lithium titanate, binding agent A and conductive agent A is (90～95): (2～5): (3～5).Described binding agent A is poly-
One in vinylidene, politef, polyvinyl alcohol.Described conductive agent A is conductive agent SP, CNT, Graphene, gas
One in phase grown carbon fiber.
The silicon layer of collection liquid surface and lithium titanate active material layer can play cooperative effect between the two, i.e. utilize silicon
The characteristic that material gram volume is high, utilizes again the characteristic that lithium titanate high rate performance is high, security performance is high, and plays between bi-material
Cooperative effect, improve the energy density of lithium ion battery, high rate performance and security performance；Meanwhile, lithium metaaluminate composite bed tool
Have good lithium ion conductive and be provided that more lithium ion tunnel, improve further lithium ion battery high rate performance and
Security performance.
Described lithium metaaluminate composite bed is made up of lithium metaaluminate, organic compounds containing nitrogen, binding agent B and conductive agent B.Aluminum partially
Acid lithium, organic compounds containing nitrogen, the mass ratio of binding agent B and conductive agent B are (75～89): (5～10): (5～10): (1～
5)。
When lithium ion battery temperature raises, organic compounds containing nitrogen can rely on the characteristic of self, quickly absorbs battery and produces
Heat, on the one hand spontaneously there is chemical reaction, generate protective layer at active material surface, can effectively suppress the temperature of battery
The continuation of degree raises；On the other hand can be passivated active material layer, from root, control the potential safety hazard of battery, ensure battery
Safety.Conductive agent in lithium metaaluminate composite bed can also improve electron conduction.
Preferably, described organic compounds containing nitrogen is melamine cyanurate, pentaerythritol phosphate tripolycyanamide
One in salt, ammonium polyphosphate or melamine pyrophosphate.Described binding agent B is Kynoar, politef, gathers
One in vinyl alcohol.Described conductive agent B is the one in CNT, Graphene, gas-phase growth of carbon fibre, white carbon black.
Technical program of the present invention also lies in a kind of above-mentioned high power capacity, high security lithium ion battery cathode composite pole piece
Preparation method, comprise the following steps:
1) use spray atomization and deposition technology that elementary silicon is deposited on the surface of collector, form silicon layer, obtain pole piece A；
2) active material slurry is coated in step 1) on the silicon layer of pole piece A that obtains, it is dried, forms active material layer,
Obtain pole piece B；
3) lithium metaaluminate slurry is coated in step 2) on the active material layer of pole piece B that obtains, it is dried, forms meta-aluminic acid
Lithium composite bed, to obtain final product.
Use spray atomization and deposition technology, when collection liquid surface depositing silicon, can be by controlling the parameters such as voltage
Depositing one layer of silicon thin film at collection liquid surface, the silicon materials utilizing its consistency deposited high reduce its silicon materials in discharge and recharge
The expansion rate of journey, while improving its capacity, improves its cycle performance.
Step 1) in, described collector is Copper Foil or copper mesh.The thickness of collector is 8～20 μm.
Step 1) in, the gas that described spray atomization and deposition technology uses is noble gas.Preferably, described noble gas
For the one in argon or helium.In spray atomization and deposition technology, elementary silicon is heated to 1500～2500 DEG C.
Step 1) in, described elementary silicon is the silica flour of particle diameter 1～25 μm.The thickness of described silicon layer is 4～6 μm.
Step 2) in, the preparation method of described active material slurry, comprise the following steps: at the N-methyl pyrrole of every 150ml
Pyrrolidone adds 90～95g lithium titanates, 2～5g binding agent A and 3～5g conductive agent A, mixing, to obtain final product.Preferably, described viscous
Knot agent A is the one in Kynoar, politef, polyvinyl alcohol.Described conductive agent A is conductive agent SP, CNT,
One in Graphene, gas-phase growth of carbon fibre.
Step 2) in, the thickness of described active material layer is 100～300 μm.
Step 3) in, the preparation method of described lithium metaaluminate slurry, comprise the following steps: at the N-methyl pyrrole of every 100ml
Pyrrolidone adds 5～10g binding agent B, is uniformly dispersed, is then sequentially added into that 1～5g conductive agent B, 5～10g is nitrogenous to organise
Compound, 75～89g lithium metaaluminate, mixing, to obtain final product.Described binding agent B is in Kynoar, politef, polyvinyl alcohol
One.Described conductive agent B is the one in CNT, Graphene, gas-phase growth of carbon fibre, white carbon black.
Step 3) in, the thickness of described lithium metaaluminate composite bed is 5～10 μm.
Technical program of the present invention also lies in a kind of employing above-mentioned high power capacity, high security lithium ion battery cathode composite pole
The lithium ion battery of sheet.
Accompanying drawing explanation
Fig. 1 is the high power capacity of embodiment 1, the structural representation of high security lithium ion battery cathode composite pole piece: 1-collection
Fluid, 2-silicon layer, 3-active material layer, 4-lithium metaaluminate composite bed；
Fig. 2 is to use the high power capacity of embodiment 1, the lithium ion battery of high security lithium ion battery cathode composite pole piece
DC internal resistance curve chart；
Fig. 3 is to use the high power capacity of embodiment 1, the lithium ion battery of high security lithium ion battery cathode composite pole piece
Multiplying power charging figure.
Detailed description of the invention
Below in conjunction with detailed description of the invention, the present invention is further illustrated.
Embodiment 1
The high power capacity of the present embodiment, high security lithium ion battery cathode composite pole piece, as it is shown in figure 1, include 1-afflux
Body, 2-silicon layer and 3-active material layer, on the surface of 1-collector along away from the direction of 1-collector, be sequentially provided with 2-silicon layer,
3-active material layer and 4-lithium metaaluminate composite bed.1-collector is Copper Foil, and thickness is 10 μm；The composition of 2-silicon layer is silicon list
Matter；3-active material layer is made up of lithium titanate, Kynoar, conductive agent SP, lithium titanate, Kynoar and conductive agent SP's
Mass ratio is 93:3:4；4-lithium metaaluminate composite bed is by lithium metaaluminate, melamine cyanurate, Kynoar and carbon nanometer
Pipe forms, and the mass ratio of lithium metaaluminate, melamine cyanurate, Kynoar and CNT is 81:8:8:3；2-silicon
Layer, 3-active material layer and 4-lithium metaaluminate composite bed thickness ratio for 5:200:8.
The high power capacity of the present embodiment, the preparation method of high security lithium ion battery cathode composite pole piece, including following step
Rapid:
1) active material slurry and lithium metaaluminate slurry are prepared:
A, in the N-Methyl pyrrolidone of every 150ml, add 93g lithium titanate, 3g Kynoar and 4g conductive agent SP,
Mix homogeneously, obtains active material slurry；
B, in the N-Methyl pyrrolidone of every 100ml add 8g Kynoar, be uniformly dispersed, be then sequentially added into 3g
CNT, 8g melamine cyanurate, 81g lithium metaaluminate, mixing, obtain lithium metaaluminate slurry；
2) the elementary silicon granule that particle diameter is 10 μm is placed in stove, uses spray atomization and deposition technology, at argon gas
In atmosphere, elementary silicon being heated to 2000 DEG C, then cooling make elementary silicon be deposited on copper foil surface that thickness is 10 μm, forms thickness
It is the silicon layer of 5 μm, obtains pole piece A；
3) coating machine is used by step 1) A) active material slurry that obtains is coated in step 2) silicon layer of the pole piece A of gained
On, it is dried, forms the active material layer that thickness is 200 μm, obtain pole piece B；
4) coating machine is used by step 1) B) the lithium metaaluminate slurry that obtains is coated in step 3) activity of the pole piece B of gained
On material layer, it is dried, forms the lithium metaaluminate composite bed that thickness is 8 μm, to obtain final product.
The lithium ion battery of the present embodiment, uses above-mentioned high power capacity, the high security lithium ion battery cathode composite pole piece to be
Negative pole, with LiNi1/3Co1/3Mn1/3O2Ternary material is positive pole, with LiPF6(solvent is EC+DEC, volume ratio 1:1, concentration
1.3mol/l) it is electrolyte, with Celgard2400 as barrier film, is assembled into 5AH soft-package battery, then fills with 0.1C multiplying power
Electricity, constant-current charge to 3.2V, discharge the gas produced in charging process, then follow to 1.0V, discharge and recharge with the multiplying power discharging of 0.1C
The gas that will produce in battery charge and discharge process after ring 2 times is discharged, and to obtain final product.
Embodiment 2
The high power capacity of the present embodiment, high security lithium ion battery cathode composite pole piece, including collector, silicon layer and activity
Material layer, on the surface of collector along the direction away from collector, is sequentially provided with silicon layer, active material layer and lithium metaaluminate compound
Layer.Collector is Copper Foil, and thickness is 8 μm；The composition of silicon layer is elementary silicon；Active material layer by lithium titanate, Kynoar, lead
Electricity agent SP composition, the mass ratio of lithium titanate, Kynoar and conductive agent SP is 90:5:5；Lithium metaaluminate composite bed is by meta-aluminic acid
Lithium, melamine salt of pentaerythritol phosphate, Kynoar and Graphene composition, lithium metaaluminate, pentaerythritol phosphate three
The mass ratio of paracyanogen amine salt, Kynoar and Graphene is 89:5:5:1；Silicon layer, active material layer and lithium metaaluminate composite bed
Thickness than for 4:100:5.
The high power capacity of the present embodiment, the preparation method of high security lithium ion battery cathode composite pole piece, including following step
Rapid:
1) active material slurry and lithium metaaluminate slurry are prepared:
A, in the N-Methyl pyrrolidone of every 150ml, add 90g lithium titanate, 5g Kynoar and 5g conductive agent SP,
Mix homogeneously, obtains active material slurry；
B, in the N-Methyl pyrrolidone of every 100ml add 5g Kynoar, be uniformly dispersed, be then sequentially added into 1g
Graphene, 5g melamine salt of pentaerythritol phosphate, 89g lithium metaaluminate, mixing, obtain lithium metaaluminate slurry；
2) the elementary silicon granule that particle diameter is 1 μm is placed in stove, uses spray atomization and deposition technology, in argon gas atmosphere
Middle elementary silicon being heated to 2000 DEG C, then cooling make elementary silicon be deposited on copper foil surface that thickness is 8 μm, forming thickness is 4 μ
The silicon layer of m, obtains pole piece A；
3) coating machine is used by step 1) A) active material slurry that obtains is coated in step 2) silicon layer of the pole piece A of gained
On, it is dried, forms the active material layer that thickness is 100 μm, obtain pole piece B；
4) coating machine is used by step 1) B) the lithium metaaluminate slurry that obtains is coated in step 3) activity of the pole piece B of gained
On material layer, it is dried, forms the lithium metaaluminate composite bed that thickness is 5 μm, to obtain final product.
The lithium ion battery of the present embodiment, uses above-mentioned high power capacity, the high security lithium ion battery cathode composite pole piece to be
Negative pole, with LiNi1/3Co1/3Mn1/3O2Ternary material is positive pole, with LiPF6(solvent is EC+DEC, volume ratio 1:1, concentration
1.3mol/l) it is electrolyte, with Celgard 2400 as barrier film, is assembled into 5AH soft-package battery, then fills with 0.1C multiplying power
Electricity, constant-current charge to 3.2V, discharge the gas produced in charging process, then follow to 1.0V, discharge and recharge with the multiplying power discharging of 0.1C
The gas that will produce in battery charge and discharge process after ring 2 times is discharged, and to obtain final product.
Embodiment 3
The high power capacity of the present embodiment, high security lithium ion battery cathode composite pole piece, including collector, silicon layer and activity
Material layer, on the surface of collector along the direction away from collector, is sequentially provided with silicon layer, active material layer and lithium metaaluminate compound
Layer.Collector is Copper Foil, and thickness is 20 μm；The composition of silicon layer is elementary silicon；Active material layer by lithium titanate, Kynoar,
Conductive agent SP forms, and the mass ratio of lithium titanate, Kynoar and conductive agent SP is 95:5:3；Lithium metaaluminate composite bed is by inclined aluminum
Acid lithium, ammonium polyphosphate (degree of polymerization is 50), Kynoar and white carbon black composition, lithium metaaluminate, ammonium polyphosphate, polyvinylidene fluoride
The mass ratio of alkene and white carbon black is 75:10:10:5；The thickness of silicon layer, active material layer and lithium metaaluminate composite bed is than for 6:300:
10。
The high power capacity of the present embodiment, the preparation method of high security lithium ion battery cathode composite pole piece, including following step
Rapid:
1) active material slurry and lithium metaaluminate slurry are prepared:
A, in the N-Methyl pyrrolidone of every 150ml, add 95g lithium titanate, 5g Kynoar and 3g conductive agent SP,
Mix homogeneously, obtains active material slurry；
B, in the N-Methyl pyrrolidone of every 100ml add 10g Kynoar, be uniformly dispersed, be then sequentially added into
5g white carbon black, 10g ammonium polyphosphate, 75g lithium metaaluminate, mixing, obtain lithium metaaluminate slurry；
2) the elementary silicon granule that particle diameter is 25 μm is placed in stove, uses spray atomization and deposition technology, at argon gas
In atmosphere, elementary silicon being heated to 2000 DEG C, then cooling make elementary silicon be deposited on copper foil surface that thickness is 20 μm, forms thickness
It is the silicon layer of 6 μm, obtains pole piece A；
3) coating machine is used by step 1) A) active material slurry that obtains is coated in step 2) silicon layer of the pole piece A of gained
On, it is dried, forms the active material layer that thickness is 300 μm, obtain pole piece B；
4) coating machine is used by step 1) B) the lithium metaaluminate slurry that obtains is coated in step 3) activity of the pole piece B of gained
On material layer, it is dried, forms the lithium metaaluminate composite bed that thickness is 10 μm, to obtain final product.
The lithium ion battery of the present embodiment, uses above-mentioned high power capacity, the high security lithium ion battery cathode composite pole piece to be
Negative pole, with LiNi1/3Co1/3Mn1/3O2Ternary material is positive pole, with LiPF6(solvent is EC+DEC, volume ratio 1:1, concentration
1.3mol/l) it is electrolyte, with Celgard2400 as barrier film, is assembled into 5AH soft-package battery, then fills with 0.1C multiplying power
Electricity, constant-current charge to 3.2V, discharge the gas produced in charging process, then follow to 1.0V, discharge and recharge with the multiplying power discharging of 0.1C
The gas that will produce in battery charge and discharge process after ring 2 times is discharged, and to obtain final product.
Embodiment 4
The high power capacity of the present embodiment, high security lithium ion battery cathode composite pole piece, including collector, silicon layer and activity
Material layer, on the surface of collector along the direction away from collector, is sequentially provided with silicon layer, active material layer and lithium metaaluminate compound
Layer.Collector is copper mesh, and thickness is 20 μm；The composition of silicon layer is elementary silicon；Active material layer by lithium titanate, politef,
CNT forms, and the mass ratio of lithium titanate, politef and CNT is 94:4:3；Lithium metaaluminate composite bed is by inclined aluminum
Acid lithium, melamine pyrophosphate, politef and gas-phase growth of carbon fibre composition, lithium metaaluminate, melamine pyrophosphoric
The mass ratio of salt, politef and gas-phase growth of carbon fibre is 85:7:9:4；Silicon layer, active material layer and lithium metaaluminate are compound
The thickness of layer ratio is for 5.5:250:6.
The high power capacity of the present embodiment, the preparation method of high security lithium ion battery cathode composite pole piece, including following step
Rapid:
1) active material slurry and lithium metaaluminate slurry are prepared:
A, in the N-Methyl pyrrolidone of every 150ml, add 94g lithium titanate, 4g politef and 3g CNT,
Mix homogeneously, obtains active material slurry；
B, in the N-Methyl pyrrolidone of every 100ml add 9g politef, be uniformly dispersed, be then sequentially added into 4g
Gas-phase growth of carbon fibre, 7g melamine pyrophosphate, 85g lithium metaaluminate, mixing, obtain lithium metaaluminate slurry；
2) the elementary silicon granule that particle diameter is 20 μm is placed in stove, uses spray atomization and deposition technology, at helium gas
In atmosphere, elementary silicon being heated to 2500 DEG C, then the surface of cooling make elementary silicon be deposited on copper mesh that thickness is 20 μm, forms thickness
Degree is the silicon layer of 5.5 μm, obtains pole piece A；
3) coating machine is used by step 1) A) active material slurry that obtains is coated in step 2) silicon layer of the pole piece A of gained
On, it is dried, forms the active material layer that thickness is 250 μm, obtain pole piece B；
4) coating machine is used by step 1) B) the lithium metaaluminate slurry that obtains is coated in step 3) activity of the pole piece B of gained
On material layer, it is dried, forms the lithium metaaluminate composite bed that thickness is 6 μm, to obtain final product.
The lithium ion battery of the present embodiment, uses above-mentioned high power capacity, the high security lithium ion battery cathode composite pole piece to be
Negative pole, with LiNi1/3Co1/3Mn1/3O2Ternary material is positive pole, with LiPF6(solvent is EC+DEC, volume ratio 1:1, concentration
1.3mol/l) it is electrolyte, with Celgard2400 as barrier film, is assembled into 5AH soft-package battery, then fills with 0.1C multiplying power
Electricity, constant-current charge to 3.2V, discharge the gas produced in charging process, then follow to 1.0V, discharge and recharge with the multiplying power discharging of 0.1C
The gas that will produce in battery charge and discharge process after ring 2 times is discharged, and to obtain final product.
Embodiment 5
The high power capacity of the present embodiment, high security lithium ion battery cathode composite pole piece, including collector, silicon layer and activity
Material layer, on the surface of collector along the direction away from collector, is sequentially provided with silicon layer, active material layer and lithium metaaluminate compound
Layer.Collector is Copper Foil, and thickness is 8 μm；The composition of silicon layer is elementary silicon；Active material layer is by lithium titanate, polyvinyl alcohol, graphite
Alkene forms, and the mass ratio of lithium titanate, polyvinyl alcohol and Graphene is 92:2:4；Lithium metaaluminate composite bed is by lithium metaaluminate, trimerization
Pyrophosphate, polyvinyl alcohol and Graphene composition, lithium metaaluminate, melamine pyrophosphate, polyvinyl alcohol and Graphene
Mass ratio be 78:6:6.5:2；The thickness of silicon layer, active material layer and lithium metaaluminate composite bed is than for 4.5:150:7.
The high power capacity of the present embodiment, the preparation method of high security lithium ion battery cathode composite pole piece, including following step
Rapid:
1) active material slurry and lithium metaaluminate slurry are prepared:
A, addition 92g lithium titanate, 2g polyvinyl alcohol and 4g Graphene, mixing in the N-Methyl pyrrolidone of every 150ml
Uniformly, active material slurry is obtained；
B, in the N-Methyl pyrrolidone of every 100ml add 6.5g polyvinyl alcohol, be uniformly dispersed, be then sequentially added into 2g
Graphene, 6g melamine pyrophosphate, 78g lithium metaaluminate, mixing, obtain lithium metaaluminate slurry；
2) the elementary silicon granule that particle diameter is 20 μm is placed in stove, uses spray atomization and deposition technology, at argon gas
In atmosphere, elementary silicon being heated to 1500 DEG C, then cooling make elementary silicon be deposited on copper foil surface that thickness is 8 μm, forming thickness is
The silicon layer of 4.5 μm, obtains pole piece A；
3) coating machine is used by step 1) A) active material slurry that obtains is coated in step 2) silicon layer of the pole piece A of gained
On, it is dried, forms the active material layer that thickness is 150 μm, obtain pole piece B；
4) coating machine is used by step 1) B) the lithium metaaluminate slurry that obtains is coated in step 3) activity of the pole piece B of gained
On material layer, it is dried, forms the lithium metaaluminate composite bed that thickness is 7 μm, to obtain final product.
The lithium ion battery of the present embodiment, uses above-mentioned high power capacity, the high security lithium ion battery cathode composite pole piece to be
Negative pole, with LiNi1/3Co1/3Mn1/3O2Ternary material is positive pole, with LiPF6(solvent is EC+DEC, volume ratio 1:1, concentration
1.3mol/l) it is electrolyte, with Celgard2400 as barrier film, is assembled into 5AH soft-package battery, then fills with 0.1C multiplying power
Electricity, constant-current charge to 3.2V, discharge the gas produced in charging process, then follow to 1.0V, discharge and recharge with the multiplying power discharging of 0.1C
The gas that will produce in battery charge and discharge process after ring 2 times is discharged, and to obtain final product.
Comparative example
The cathode pole piece of comparative example is made up of collector and the active material layer being arranged on collection liquid surface.Collector is
Copper Foil；Active material layer is made up of lithium titanate, Kynoar, conductive agent SP, lithium titanate, Kynoar and conductive agent SP's
Mass ratio is 93:3:4.
The preparation method of the cathode pole piece of comparative example: by 93g lithium titanate, 3g Kynoar, 4g conductive agent SP and
150mlN-methyl pyrrolidone mix homogeneously obtains active material slurry, and the active substance obtained is coated in the copper of 10 microns
On paper tinsel surface, it is dried, obtains cathode pole piece.
The lithium ion battery of the present embodiment, uses above-mentioned high power capacity, the high security negative electrode of lithium titanate battery composite pole piece to be
Negative pole, with LiNi1/3Co1/3Mn1/3O2Ternary material is positive pole, with LiPF6(solvent is EC+DEC, volume ratio 1:1, concentration
1.3mol/l) being electrolyte, with Celgard 2400 as barrier film, assemble, be then charged with 0.1C multiplying power, constant-current charge is extremely
3.2V, discharges the gas produced in charging process, then with the multiplying power discharging of 0.1C to 1.0V, by battery after charge and discharge cycles 2 times
The gas produced in charge and discharge process is discharged, and to obtain final product.
Experimental example 1
The cycle performance test of lithium ion battery
Method of testing: by embodiment 1～5 and the lithium ion battery prepared of comparative example, in charging/discharging voltage scope 1.5～
2.8V, temperature 25 ± 3.0 DEG C, under conditions of charge-discharge magnification is 2.0C/2.0C, the cycle performance of test lithium ion battery.Survey
Test result is shown in Table 1.
Table 1 embodiment compares with the cycle performance of lithium ion battery of comparative example
| Project | Initial capacity (Ah) | Capacity (Ah) after 2000 times | Capability retention (%) after 2000 times |
| Embodiment 1 | 7.28 | 6.65 | 91.4 |
| Embodiment 2 | 7.26 | 6.57 | 90.5 |
| Embodiment 3 | 7.21 | 6.49 | 90.1 |
| Embodiment 4 | 7.25 | 6.51 | 89.8 |
| Embodiment 5 | 7.16 | 6.38 | 89.2 |
| Comparative example | 7.31 | 6.09 | 83.4 |
As can be seen from Table 1, using the cycle performance of the lithium ion battery of embodiment 1～5 to be substantially better than comparative example, it is former
Because the cathode pole piece that comparative example is used is to be applied directly on collector, active material slurry due to active substance
Grain is relatively big, and the contact at collector and active substance is point cantact, and resistance is relatively big, causes internal heat skewness to weigh, and real
The negative pole composite pole piece of the lithium ion battery executing example 1～5 is provided with silicon layer between collector and active material layer, can increase collection
Fluid and silicon layer, the contact area between silicon layer and active material layer, it is to avoid collector is corroded, improves following of lithium ion battery
Ring performance.Meanwhile, lithium metaaluminate composite bed has the characteristic that lithium ion conducting rate is high, in cyclic process, can accelerate lithium from
The transfer rate of son, and electrolyte and lithium titanate can directly separate by lithium metaaluminate composite bed, reduces the generation of side reaction,
Improve the cycle performance of lithium ion battery.
Experimental example 2
The DC internal resistance test of lithium ion battery
Assay method is: 1) with 0.2C5A constant current, 2.8V pressure limiting, to embodiment 1～5 and the lithium ion battery of comparative example enter
Column criterion is charged；2) with 0.2C5A constant-current discharge to 10%DOD；3) carry out constant current with big current versus cell and fill (generally 1C5A)
Experiment；4) step 1 is repeated)～3), each depth of discharge increases by 10%, until depth of discharge is 90%；5) with 0.2C5A constant current
Electric discharge, makes battery discharge completely to final voltage 1.6V.Test result is shown in Table 2.The DC internal resistance of the lithium ion battery of embodiment 1
Curve chart is shown in Fig. 2.
The DC internal resistance of the lithium ion battery of table 2 embodiment and comparative example compares
As shown in Table 2, under the conditions of different depth of discharges, compare the lithium ion battery of comparative example, the lithium of embodiment 1～5 from
The DC internal resistance of sub-battery is reduced, and reason is: in the lithium metaaluminate composite bed of negative pole composite pole piece, lithium metaaluminate has
Well ionic conductivity, improves the conduction velocity of lithium ion, and CNT can improve electron conduction, and at active matter
The silicon layer arranged between matter layer and collector is conducive to increasing the contact area between active material layer and collector, thus reduces lithium
The internal resistance of ion battery.
Experimental example 3
The multiplying power charging performance test of lithium ion battery
Multiplying power charging method: charge with 0.5C multiplying power respectively, 0.5C discharges；2.0C multiplying power is charged, and 0.5C discharges；5.0C again
Rate is charged, and 0.5C discharges；10C multiplying power is charged, and 0.5C discharges.According to each charging modes, software calculates multiplying power charging automatically
Time.Charging/discharging voltage scope: 1.5V～2.7V.Test result is shown in Table 3.The multiplying power charging figure of the lithium ion battery of embodiment 1
See Fig. 3.
The multiplying power charging performance of the lithium ion battery of table 3 embodiment and comparative example
As shown in Table 3, in embodiment 1～5, the multiplying power charging performance of lithium ion battery is substantially better than comparative example, when i.e. charging
Between shorter, reason is: need the migration of lithium ion in battery charging process, and lithium metaaluminate composite bed and active material layer energy
Thering is provided sufficient lithium ion, and the lithium metaaluminate in lithium metaaluminate composite bed has good lithium ion conducting performance, carbon is received
Mitron can improve electron conduction, thus shortens the charging interval, improves the multiplying power charging performance of battery.
Experimental example 4
Fastening lithium ionic cell performance test
1) making of fastening lithium ionic cell: respectively with embodiment 1～5 negative pole composite pole piece and the negative pole pole of comparative example
Sheet, is below in the glove box of 0.1ppm being assembled into button cell at oxygen and water content, wherein, electrode is used lithium sheet,
Barrier film is Celgard 2400, and electrolyte solute is the LiPF of 1mol/L6, solvent is ethylene carbonate (EC) and diethyl carbonate
(DMC) mixed solution of (volume ratio is 1:1)；
2) method of testing: by 1) in the button cell that obtains be respectively pivoted on blue electric tester, with the multiplying power charge and discharge of 0.1C
Electricity, voltage range is 1.0V～2.8V, stopping after circulating 3 weeks, and the discharge capacity first recorded and first efficiency are shown in Table 4.
Table 4 embodiment and the button cell Performance comparision of comparative example
| Project | Discharge capacity (mAH/g) first | Efficiency (%) first |
| Embodiment 1 | 182.5 | 97.6 |
| Embodiment 2 | 180.6 | 97.1 |
| Embodiment 3 | 180.3 | 96.8 |
| Embodiment 4 | 179.5 | 96.4 |
| Embodiment 5 | 178.3 | 96.1 |
| Comparative example | 144.4 | 94.2 |
As can be seen from Table 4, the lithium titanate anode pole piece that embodiment 1～5 is prepared is at gram volume with first in terms of efficiency
Substantially due to comparative example, its reason is, at the silicon materials of collection liquid surface deposition high power capacity, can improve whole cathode pole piece
Gram volume, simultaneously when preparing negative pole composite pole piece, uses spray atomization and deposition technology deposited silicon layer on collection liquid surface, makes
Obtain the adhesion between silicon and collector preferable, improve the transfer rate of electronics, thus improve the gram volume of its cathode pole piece
Play, and improve its efficiency first.Meanwhile, containing sufficient lithium ion in outer layer lithium metaaluminate, for charge and discharge process is formed
The lithium ion that SEI consumes provides sufficient lithium ion, improves its efficiency first further.
Claims (10)
1. a high power capacity, high security lithium ion battery cathode composite pole piece, it is characterised in that: include collector, silicon layer and
Active material layer, on the surface of collector along the direction away from collector, is sequentially provided with silicon layer, active material layer and lithium metaaluminate
Composite bed.
High power capacity the most according to claim 1, high security lithium ion battery cathode composite pole piece, it is characterised in that: institute
State the thickness of silicon layer, active material layer and lithium metaaluminate composite bed than being (4～6): (100～300): (5～10).
High power capacity the most according to claim 1, high security lithium ion battery cathode composite pole piece, it is characterised in that: institute
The composition stating silicon layer is elementary silicon.
High power capacity the most according to claim 1, high security lithium ion battery cathode composite pole piece, it is characterised in that: institute
The active substance stating active material layer is lithium titanate.
High power capacity the most according to claim 1, high security lithium ion battery cathode composite pole piece, it is characterised in that: institute
State lithium metaaluminate composite bed to be made up of lithium metaaluminate, organic compounds containing nitrogen, binding agent B and conductive agent B.
High power capacity the most according to claim 5, high security lithium ion battery cathode composite pole piece, it is characterised in that: institute
The organic compounds containing nitrogen stated is melamine cyanurate, melamine salt of pentaerythritol phosphate, ammonium polyphosphate or three
One in poly cyanamid pyrophosphate.
High power capacity the most according to claim 5, high security lithium ion battery cathode composite pole piece, it is characterised in that: institute
Stating binding agent B is the one in Kynoar, politef, polyvinyl alcohol；Described conductive agent B is CNT, graphite
One in alkene, gas-phase growth of carbon fibre, white carbon black.
8. a high power capacity as described in any one in claim 1～7, high security lithium ion battery cathode composite pole piece
Preparation method, it is characterised in that: comprise the following steps:
1) use spray atomization and deposition technology, elementary silicon is deposited on the surface of collector, form silicon layer, obtain pole piece A；
2) active material slurry is coated in step 1) on the silicon layer of pole piece A that obtains, it is dried, forms active material layer, obtain
Pole piece B；
3) lithium metaaluminate slurry is coated in step 2) on the active material layer of pole piece B that obtains, it is dried, forms lithium metaaluminate multiple
Close layer, to obtain final product.
High power capacity the most according to claim 8, the preparation method of high security lithium ion battery cathode composite pole piece, it is special
Levy and be: step 1) in, described elementary silicon is the silica flour of particle diameter 1～25 μm.
10. one kind uses high power capacity as claimed in claim 1, the lithium ion of high security lithium ion battery cathode composite pole piece
Battery.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108598358A (en) * | 2018-04-24 | 2018-09-28 | 中航锂电技术研究院有限公司 | A kind of preparation method of composition metal cathode of lithium |
| CN109698359A (en) * | 2018-11-26 | 2019-04-30 | 中航锂电技术研究院有限公司 | It is a kind of with electricity interconnection, the composite current collector and preparation method thereof of through-hole structure, battery pole piece and lithium ion battery |
| CN109786665A (en) * | 2018-12-20 | 2019-05-21 | 上海力信能源科技有限责任公司 | A kind of silicon-carbon composite cathode pole piece and preparation method thereof |
| CN109802095A (en) * | 2019-01-31 | 2019-05-24 | 哈尔滨体育学院 | It is a kind of in the pole piece of surface coated conductive layer and its lithium battery of preparation |
| CN112151757A (en) * | 2020-09-22 | 2020-12-29 | 浙江锋锂新能源科技有限公司 | Negative plate with multilayer film structure and mixed solid-liquid electrolyte lithium storage battery thereof |
| CN113421999A (en) * | 2021-06-21 | 2021-09-21 | 宁德新能源科技有限公司 | Electrochemical device and electronic device |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103117382A (en) * | 2013-02-25 | 2013-05-22 | 江苏乐能电池股份有限公司 | Lithium ion battery negative pole material capable of improving safety performance and preparation method thereof |
| CN105118970A (en) * | 2015-10-14 | 2015-12-02 | 中航锂电（洛阳）有限公司 | Lithium ion battery composite pole piece, preparation method thereof and lithium ion battery |
-
2016
- 2016-08-29 CN CN201610754676.9A patent/CN106252598B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103117382A (en) * | 2013-02-25 | 2013-05-22 | 江苏乐能电池股份有限公司 | Lithium ion battery negative pole material capable of improving safety performance and preparation method thereof |
| CN105118970A (en) * | 2015-10-14 | 2015-12-02 | 中航锂电（洛阳）有限公司 | Lithium ion battery composite pole piece, preparation method thereof and lithium ion battery |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108598358A (en) * | 2018-04-24 | 2018-09-28 | 中航锂电技术研究院有限公司 | A kind of preparation method of composition metal cathode of lithium |
| CN109698359A (en) * | 2018-11-26 | 2019-04-30 | 中航锂电技术研究院有限公司 | It is a kind of with electricity interconnection, the composite current collector and preparation method thereof of through-hole structure, battery pole piece and lithium ion battery |
| CN109786665A (en) * | 2018-12-20 | 2019-05-21 | 上海力信能源科技有限责任公司 | A kind of silicon-carbon composite cathode pole piece and preparation method thereof |
| CN109802095A (en) * | 2019-01-31 | 2019-05-24 | 哈尔滨体育学院 | It is a kind of in the pole piece of surface coated conductive layer and its lithium battery of preparation |
| CN112151757A (en) * | 2020-09-22 | 2020-12-29 | 浙江锋锂新能源科技有限公司 | Negative plate with multilayer film structure and mixed solid-liquid electrolyte lithium storage battery thereof |
| CN113421999A (en) * | 2021-06-21 | 2021-09-21 | 宁德新能源科技有限公司 | Electrochemical device and electronic device |
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