CN106876660A - A kind of lithium ion battery piezoelectricity positive pole composite pole piece and its lithium ion battery applications - Google Patents
A kind of lithium ion battery piezoelectricity positive pole composite pole piece and its lithium ion battery applications Download PDFInfo
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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
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
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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
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/621—Binders
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
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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
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention belongs to lithium ion battery preparation field, specifically a kind of lithium ion battery piezoelectricity positive pole composite pole piece and its lithium ion battery, its positive pole composite pole piece is made up of anode pole piece with the piezoelectric ceramics composite bed for being coated in surface, and prepares positive pole Piezoelectric anisotropy pole piece by electric field polarization treatment.Piezoelectricity positive pole composite pole piece of the invention is applied to lithium ion battery, electric discharge is carried out with the battery when battery pole piece is squeezed improve its security performance, improve the transmission rate of lithium ion in its lithium ion charge and discharge process simultaneously, and improve its lithium ion battery fill ability and its high rate performance soon.
Description
Technical field
The invention belongs to lithium ion battery preparation field, particularly a kind of lithium ion battery piezoelectricity positive pole composite pole piece and
Its lithium ion battery applications.
Background technology
Lithium rechargeable battery with its energy density it is high, have extended cycle life, advantages of environment protection and be subject to the green grass or young crops of people
Look at, and lithium ion battery safety performance be determine battery can popularization and application key point.Current lithium battery be primarily present with
Lower potential safety hazard：The lithium metal that internal short-circuit of battery, external short circuit and super-charge super-discharge cause is separated out, and can cause battery to fire
Burn.For the security performance for improving battery is mainly arranged by using ceramic diaphragm, feature electrolyte and its pole piece paint-on technique etc.
While applying to improve the security performance of battery, but there is security performance raising, cycle performance of battery is adversely affected,
Or the cycle performance of raising battery, the security performance of battery is had influence on, a kind of while security performance is improved, electricity is badly in need of at present
The chemical property in pond is unaffected or the preparation method that is improved.
Patent（CN105449159 A）Disclose based lithium-ion battery positive plate and its making side of a kind of high safety performance
Method, it mainly coats oxide ceramic layer on positive electrode material layer, to improve the security performance of its lithium ion battery.Its principle master
If on the one hand have selected oxide ceramic material as coating material, the generation of battery short circuit is effectively reduced, work as battery
When being short-circuited, the accumulation of pole piece heat can be completely cut off, prevent the further thermal runaway of pole piece；On the other hand, to coating material
Material oxide ceramic powder body is processed, and controls its grain size, and cell interface impedance is greatly reduced, and is additionally provided electronics
Transmission tunnel, has isolated directly contact of the electrolyte to positive electrode, reduces the generation of electrolyte and positive electrode side reaction,
And the Volume Changes during lithium ion deintercalation can be accommodated, the destruction of electrode structure is prevented, also to oxide ceramic powder body
Pulping process and system are controlled, and slurry dispersion homogeneity are improve, while the micro of ceramic powder can be prevented effectively
Come off, on the premise of battery security is effectively ensured, the chemical property to battery itself is not also impacted, but above-mentioned
Method is under squeezed state in battery, and the security performance to lithium ion battery improves amplitude less, while the oxygen of its coat
Compound ceramic material functions only as isolation heat and improves its heat dispersion, and improvement is had no to cycle performance.Therefore one is developed
Plant the electrodes of lithium-ion batteries that security performance is high, cycle performance is good and seem extremely important, and be applied to lithium ion battery.
The content of the invention
For the defect of the aspects such as current lithium ion battery safety performance difference, the purpose of the present invention is by paint-on technique just
Pole pole piece coats piezoceramic material to improve the security performance of its lithium ion battery.
The technical scheme is that：A kind of lithium ion battery piezoelectricity positive pole composite pole piece, positive pole composite pole piece is by just
Pole pole piece and the piezoelectric ceramics composite bed composition for being coated in anode pole piece surface, are processed by electric field polarization and prepare positive pole piezoelectricity
Composite pole piece, it is characterised in that：Described piezoelectric ceramics composite bed thickness is 1~10 μm,；Piezoelectric ceramics composite bed is made pottery by piezoelectricity
Ceramic material, binding agent, conductive agent, surfactant are constituted, and mass ratio is：60~80：10~20:1~10：1~10.
Described conductive agent is the one kind in graphene oxide, hollow carbon sphere, gas-phase growth of carbon fibre, CNT；Pressure
Electroceramics material is in barium titanate, lead titanates, zirconium metatitanic acid, lead zirconate titanate, magnoniobate, lead magnesio-niobate, lead niobic acid, lead tantanate
Kind；Surfactant is the one kind in APG, amine-oxides, glyceride or alkylolamides.
Described binding agent is made up of Kynoar and polystyrene carbonic ester, and its mass ratio is 80~90：10~20.
Preparation method of the invention is comprised the following steps：1）Prepare piezoelectric ceramics composite mortar；2）Prepare anode pole piece；3）
Prepare piezoelectricity positive pole composite pole piece；It is characterized in that：
1）, prepare binder solution：Take Kynoar that mass ratio is 8~9 parts and 1~2 part of polystyrene carbonic ester adds
It is added in 500 parts of 1-METHYLPYRROLIDONEs, the binder solution that concentration is 10% is obtained after being uniformly dispersed；
2）, prepare piezoelectric ceramics composite mortar；Weigh 10~20 parts of binder solutions of above-mentioned solid masses, 1~10 part of conductive agent,
1~10 part of surfactant-dispersed is uniform, then adds 60~80 parts of piezoceramic materials, and is uniformly dispersed by ball mill, obtains
To piezoelectric ceramics composite mortar；
3）, prepare anode pole piece：Weigh during 4~6 parts of Kynoar are dissolved in 200 parts of 1-METHYLPYRROLIDONE and be uniformly dispersed
Afterwards, then 4~6 parts of conductive agents and its 88~92 parts of LiNi1/3Co1/3Mn1/3O are added2Ternary material prepares slurry, passes through
Slurry is coated in positive pole aluminium foil collector A upper surfaces by coating machine, obtains containing active material in collector A upper surfaces after drying
The anode pole piece of layer B；
4）, piezoelectric ceramics composite mortar is sprayed on by anode pole piece surface by intaglio press, drying is contained after finishing
The positive pole composite pole piece of piezoceramics layer C, coating thickness is 1~10 μm；Afterwards at a temperature of 100~150 DEG C, by composite pole
Piece is placed in parallel-plate electric field, and polarize 1~3min under the voltage of 6~20kV/mm, finally obtains piezoelectricity positive pole composite pole piece.
A kind of described lithium ion battery piezoelectricity positive pole composite pole piece, is applied to lithium ion battery.
Beneficial effects of the present invention：1st, when lithium ion battery is squeezed, the piezoelectric ceramics in positive pole composite pole piece is applied
Coating can realize electric discharge, improve the security performance of its lithium ion battery；And with reference to the conductive agent in ceramic layer improve its lithium from
The conduction velocity of son and its electronics；And make its binding agent have stability strong in a high voltage state using its high pressure binding agent, glue
Attached power is strong and its low advantage of expansion rate.2nd, electric field treatment is carried out by pole piece, makes the electricdomain in Piezoelectric Ceramic Coatings along pole
Change electric field orientation arrangement, form electric field alignment direction, improve the transmission rate of its lithium ion and its structural stability of pole piece, and
Improve the cycle performance of pole piece.
Brief description of the drawings
The pole piece structure schematic diagram of Fig. 1, embodiment；
Wherein：A-collector, B-active material layer, C-piezoelectric ceramics composite bed.
Fig. 2, embodiment compare figure with the cyclic curve of comparative example.
Specific embodiment
A kind of lithium ion battery piezoelectricity positive pole composite pole piece, by anode pole piece and the piezoelectric ceramics composite bed for being coated in surface
Composition, piezoelectric ceramics composite bed thickness is 1~10 μm, is processed by electric field polarization and prepares positive pole Piezoelectric anisotropy pole piece；It is described
Piezoelectric ceramics composite bed be made up of piezoceramic material, binding agent, conductive agent, surfactant, its mass ratio is：60~
80：10~20:1~10：1~10.
Embodiment 1：
The preparation of lithium ion battery piezoelectricity positive pole composite pole piece：
Weigh 8.5g Kynoar and 1.5g polystyrene carbonic esters are added in 500gN- crassitudes, after being uniformly dispersed
Obtain binder solution；1.5 times of binder solution is weighed afterwards, and adds 5g graphene oxides and its 5g APGs, and
It is uniformly dispersed, 70g barium titanate ceramics materials is added afterwards, and be uniformly dispersed by ball mill, obtains piezoelectric ceramics composite mortar；
Weigh simultaneously after 5g Kynoar is dissolved in the 1-METHYLPYRROLIDONE of 200g and is uniformly dispersed, then to add 5gSP conductive
Agent and its 90gLiNi1/3Co1/3Mn1/3O2 ternary materials prepare slurry, and slurry is coated in into positive pole aluminium by coating machine afterwards
Paper tinsel collector A upper surfaces, the anode pole piece containing active material layer B is obtained above after drying in collector A；
Piezoelectric ceramics composite mortar is sprayed on by anode pole piece surface by intaglio press afterwards, drying is contained after finishing
The positive pole composite pole piece of piezoceramics layer C, its coating thickness is 5 μm；Afterwards at a temperature of 120 DEG C, by the composite pole piece
It is placed in parallel-plate electric field, polarize 2min under the voltage of 10kV/mm, finally obtains piezoelectricity positive pole composite pole piece.
Embodiment 2：
Weigh 8.0g Kynoar and 2.0g polystyrene carbonic esters are added in 500gN- crassitudes, after being uniformly dispersed
Obtain binder solution；Above-mentioned binder solution is weighed afterwards, and adds 1g gas-phase growth of carbon fibre and its 1g amine-oxides, and
It is uniformly dispersed, 80g lead titanate ceramics materials is added afterwards, and be uniformly dispersed by ball mill, obtains piezoelectric ceramics composite mortar；
Weigh simultaneously after 5g Kynoar is dissolved in the 1-METHYLPYRROLIDONE of 200g and is uniformly dispersed, then to add 5gSP conductive
Agent and its 90gLiNi1/3Co1/3Mn1/3O2 ternary materials prepare slurry, and slurry is coated in into positive pole aluminium by coating machine afterwards
Paper tinsel collector A upper surfaces, the anode pole piece containing active material layer B is obtained after drying in collection liquid surface；
Piezoelectric ceramics composite mortar is sprayed on by anode pole piece surface by intaglio press afterwards, drying is contained after finishing
The positive pole composite pole piece of piezoceramics layer C, coating thickness is 1 μm；Afterwards at a temperature of 100 DEG C, the composite pole piece is put
In parallel-plate electric field, polarize 3min under the voltage of 20kV/mm, finally obtains piezoelectricity positive pole composite pole piece.
Embodiment 3：
Weigh 9.0g Kynoar and 1.0g polystyrene carbonic esters are added in 500gN- crassitudes, after being uniformly dispersed
Obtain binder solution；2 times of binder solution is weighed afterwards, and adds 10g CNTs and its 10g glyceride, and disperse
Uniformly, 60g lead magnesio-niobate ceramics materials are added afterwards, and is uniformly dispersed by ball mill, obtain piezoelectric ceramics composite mortar；
Weigh simultaneously after 5g Kynoar is dissolved in the 1-METHYLPYRROLIDONE of 200g and is uniformly dispersed, then to add 5gSP conductive
Agent and its 90gLiNi1/3Co1/3Mn1/3O2 ternary materials prepare slurry, and slurry is coated in into positive pole aluminium by coating machine afterwards
Paper tinsel collector A upper surfaces, the anode pole piece containing active material layer B is obtained after drying in collection liquid surface；
Piezoelectric ceramics composite mortar is sprayed on by anode pole piece surface by intaglio press afterwards, drying is contained after finishing
The positive pole composite pole piece of piezoceramics layer C.Coating thickness is 10 μm；Afterwards at a temperature of 150 DEG C, the composite pole piece is put
In parallel-plate electric field, polarize 1min under the voltage of 6kV/mm, finally obtains piezoelectricity positive pole composite pole piece.
Comparative example：
Weigh simultaneously after 5g Kynoar is dissolved in the 1-METHYLPYRROLIDONE of 200g and is uniformly dispersed, then to add 5gSP conductive
Agent and its 90gLiNi1/3Co1/3Mn1/3O2 ternary materials prepare slurry, and slurry is coated in into positive pole aluminium by coating machine afterwards
Paper tinsel collector A upper surfaces, the anode pole piece containing active material layer B is obtained after drying in collection liquid surface.
1）SEM is tested：
SEM tests are carried out to the pole piece that embodiment 1 is prepared, it is smooth by can be seen that pole piece in Fig. 1, and by material
Section can be seen that active material surface and be coated with one layer of uniform ceramic layer；
2）Electrochemical property test：
Positive plate in Example 1-3 and comparative example, Delanium is active material, and electrolyte is LiPF6/ EC+DEC (volumes
Than 1:1) solution, concentration 1.3mol/L, barrier film is the films of Celgard 2400, prepares 5AH soft-package batteries A1, A2, A3 and its B1.
The suction of the imbibition ability and soft-package battery A1, A2, A3 and its B1 of testing example 1-3 and comparative example pole piece afterwards
Liquid liquid-keeping property, high temperature cyclic performance（1.0C/1.0C, 55 DEG C）, DC internal resistance, security performance.Method of testing is marked with reference to country
Quasi- GB/T 18287-2000《Standard lithium ion test request》.
The assay method of DC internal resistance is：1）With 0.2C5A constant currents, 4.2V pressure limitings, carry out standard and fill to lithium ion battery
Electricity；2）With 0.2C5A constant-current discharges are to 10%DOD；3）Constant current is carried out with high current to battery to fill（Generally 1C5A）Experiment；4）Weight
Multiple step 1）-3）, each depth of discharge increases by 10%, until depth of discharge is 90%；5）With 0.2C5A constant-current discharges to terminating electricity
Pressure 2.5V makes battery discharge completely.
Test result see the table below 1-5 and accompanying drawing 1-2.
The imbibition ability of the positive plate of table 1
| Project | Rate of liquid aspiration（mL/min） | Protect liquid rate（24h electrolyte contents/0h electrolyte contents） |
| Embodiment 1 | 4.1 | 93.1% |
| Embodiment 2 | 3.8 | 92.3% |
| Embodiment 3 | 3.7 | 92.2% |
| Comparative example | 2.3 | 83.1% |
As shown in Table 1, the imbibition liquid-keeping property of positive plate is significantly better than that comparative example in embodiment 1-3, and analysis reason is：Pressure
There is material larger hole to improve its imbibition ability, and its electric conduction of carbon fiber agent specific surface area high in electroceramics layer, can be big
Width improves the imbibition liquid-keeping property of pole piece.
The cycle performance of the soft-package battery of table 2
From table 3, Fig. 2, the high temperature cyclic performance of soft-package battery is significantly better than that comparative example in embodiment 1-3, analyzes reason
It is：Piezoceramic material has heat dispersion higher, makes its battery that the thermal diffusivity of its battery is improved in charge and discharge process
Can, be conducive to the stabilization inside battery structure, so as to improve the cycle performance of battery.
Acupuncture short-circuit test：Method of testing is shown in UL2054 safety standard testing standards, as a result see the table below 1.
Table 3 is compared using the performance of lithium ion battery of the positive plate of the anode composite piece and comparative example of embodiment
| Project | DC internal resistance（mΩ） | Safety loading coefficient |
| Embodiment 1 | 4.58 | 9/10 |
| Embodiment 2 | 4.65 | 8/10 |
| Embodiment 3 | 4.69 | 8/10 |
| Comparative example | 6.99 | 4/10 |
From table 3 it can be seen that relative to comparative example, being had using the lithium ion battery of the anode composite piece of embodiment 1-3 relatively low
DC internal resistance, safety loading coefficient high.Reason is：The present invention is laminated electroceramics in anode pole piece surface coating one, makes it
When extrusion process is run into, material can be discharged battery in time, reduce its thermal runaway, improve its security performance；Press simultaneously
There is electroceramics layer high temperature resistant and heat dispersion higher equally to improve its security performance.Simultaneously because having electricity in piezoelectric
Field-effect, improves the transfer rate of lithium ion, reduces its internal resistance.
Claims (5)
1. a kind of lithium ion battery piezoelectricity positive pole composite pole piece, positive pole composite pole piece is by anode pole piece and is coated in anode pole piece
The piezoelectric ceramics composite bed composition on surface, is processed by electric field polarization and prepares positive pole Piezoelectric anisotropy pole piece, it is characterised in that：Institute
The piezoelectric ceramics composite bed thickness stated is 1~10 μm,；Piezoelectric ceramics composite bed by piezoceramic material, binding agent, conductive agent,
Surfactant is constituted, and mass ratio is：60~80：10~20:1~10：1~10.
2. described a kind of lithium ion battery piezoelectricity positive pole composite pole piece according to claim 1, it is characterised in that：Described leads
Electric agent is the one kind in graphene oxide, hollow carbon sphere, gas-phase growth of carbon fibre, CNT；Piezoceramic material is metatitanic acid
One kind in barium, lead titanates, zirconium metatitanic acid, lead zirconate titanate, magnoniobate, lead magnesio-niobate, lead niobic acid, lead tantanate；Surfactant is
One kind in APG, amine-oxides, glyceride or alkylolamides.
3. described a kind of lithium ion battery piezoelectricity positive pole composite pole piece according to claim 1, it is characterised in that：Described is viscous
Knot agent is made up of Kynoar and polystyrene carbonic ester, and its mass ratio is 80~90：10~20.
4. a kind of method of the lithium ion battery piezoelectricity positive pole composite pole piece prepared described in claim 1, comprises the following steps：1）
Prepare piezoelectric ceramics composite mortar；2）Prepare anode pole piece；3）Prepare piezoelectricity positive pole composite pole piece；It is characterized in that：
1）, prepare binder solution：Take Kynoar that mass ratio is 8~9 parts and 1~2 part of polystyrene carbonic ester adds
It is added in 500 parts of 1-METHYLPYRROLIDONEs, the binder solution that concentration is 10% is obtained after being uniformly dispersed；
2）, prepare piezoelectric ceramics composite mortar；Weigh 10~20 parts of binder solutions of above-mentioned solid masses, 1~10 part of conductive agent,
1~10 part of surfactant-dispersed is uniform, then adds 60~80 parts of piezoceramic materials, and is uniformly dispersed by ball mill, obtains
To piezoelectric ceramics composite mortar；
3）, prepare anode pole piece：Weigh during 4~6 parts of Kynoar are dissolved in 200 parts of 1-METHYLPYRROLIDONE and be uniformly dispersed
Afterwards, then 4~6 parts of conductive agents and its 88~92 parts of LiNi1/3Co1/3Mn1/3O are added2Ternary material prepares slurry, passes through
Slurry is coated in positive pole aluminium foil collector A upper surfaces by coating machine, obtains containing active material layer on collector A surfaces after drying
The anode pole piece of B；
4）, piezoelectric ceramics composite mortar is sprayed on by anode pole piece surface by intaglio press, drying is contained after finishing
The positive pole composite pole piece of piezoceramics layer C, coating thickness is 1~10 μm；Afterwards at a temperature of 100~150 DEG C, by composite pole
Piece is placed in parallel-plate electric field, and polarize 1~3min under the voltage of 6~20kV/mm, finally obtains piezoelectricity positive pole composite pole piece.
5. a kind of lithium ion battery piezoelectricity positive pole composite pole piece according to claim 1-4, is applied to lithium ion battery.
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| CN107706005A (en) * | 2017-10-13 | 2018-02-16 | 浙江萨科能源科技有限公司 | A kind of preparation method for the electrode of super capacitor that can reduce leakage current |
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| CN110400904A (en) * | 2019-06-04 | 2019-11-01 | 江西力能新能源科技有限公司 | A kind of composite ceramic coat lithium battery positive-negative plate and lithium battery |
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Application publication date: 20170620 |