CN109585840A - A kind of lithium ion battery and preparation method thereof - Google Patents
A kind of lithium ion battery and preparation method thereof Download PDFInfo
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- CN109585840A CN109585840A CN201811319324.6A CN201811319324A CN109585840A CN 109585840 A CN109585840 A CN 109585840A CN 201811319324 A CN201811319324 A CN 201811319324A CN 109585840 A CN109585840 A CN 109585840A
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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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements 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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
- H01M10/0587—Construction or manufacture of accumulators having only wound construction elements, i.e. wound positive electrodes, wound negative electrodes and wound separators
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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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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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
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
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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
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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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The invention discloses a kind of lithium ion batteries and preparation method thereof, the anode of the lithium ion battery uses high pressure lithium cobaltate cathode active material, cathode is using carbonaceous mesophase spherules graphite as active material, and diaphragm is sequentially stacked the base membrane layer to be formed using tri- layers of basement membrane of PP, PE, PP and the ceramic material coat on base membrane layer is constituted.In the above manner, lithium ion battery of the present invention effectively can mutually inhibit the thermal runaway of battery caused by 1C charging 10V overcharge of the battery at different ambient temperatures (such as 5 DEG C, 25 DEG C, 50 DEG C etc.), on fire, the explosion of battery are prevented；Simultaneously its can take into account heavy impact, thermal shock, short circuit, needle thorn, squeeze etc. it is destructive collide it is not on fire, do not explode, security performance is high.
Description
Technical field
The present invention relates to battery technology fields, and in particular to a kind of lithium ion battery and preparation method thereof.
Background technique
Lithium ion battery has been widely used all trades and professions, especially flexible packing lithium ion polymer battery, because of size, structure
Diversification and sufficiently applied, as smart phone, tablet computer, laptop, handset products, intelligence wearing produce
The frontier science and technology such as product field.But flexible packing lithium ion polymer battery product is used with the popularization of application field and terminal user
The requirement of experience is higher and higher, and the security performance requirement of flexible-packaged lithium lithium ion polymer battery itself is also higher and higher, especially
It is overcharging resisting electrical property under various circumstances.Current flexible packing lithium ion battery is to meet through 5V~10V to power on
Pressure overcharges requirement on electric performance, usually by the additive (such as BP, CHB) of addition overcharging resisting electricity in the electrolytic solution to realize,
Electrochemical reaction when participating in overcharge by additive inhibits battery thermal runaway, to play the role of overcharging resisting.But it overcharges
Additive side reaction is larger, can serious deterioration battery high-temperature, storage, cycle performance.High safety unmature in industry at present
Performance products, therefore there is an urgent need to a kind of lithium ion batteries of high safety performance.
Summary of the invention
In order to solve the above technical problem, the present invention provides a kind of lithium ion batteries and preparation method thereof.
The technical scheme adopted by the invention is that: a kind of lithium ion battery, including positive plate, negative electrode tab, diaphragm, it is described every
Film is set between the positive plate and the negative electrode tab；
The positive plate includes plus plate current-collecting body and the positive electrode material layer on the plus plate current-collecting body, the anode material
The raw material of the bed of material includes positive electrode active materials, positive conductive agent and positive electrode binder, and the positive electrode active materials include cobalt acid lithium
Positive electrode active materials, the lithium cobaltate cathode active material are high voltage lithium cobaltate cathode active material.
Will appear structural breakdown since conventional cobalt acid lithium takes off when lithium is more than 50% and discharge heat, probably for 138~
197 DEG C begin to decompose, and it is lower to take off lithium ratio more high decomposition temperature.And the positive electrode active materials of the application lithium ion battery use
High voltage lithium cobaltate cathode active material, the high voltage lithium cobaltate cathode active material are typically greater than the high voltage cobalt of 4.2V
Sour lithium positive electrode active materials, it is, the charge cutoff voltage of lithium ion battery be greater than 4.2V, specifically can be selected 4.35V,
At least one of 4.4V, 4.45V, 4.5V high voltage lithium cobaltate cathode active material.
The above high voltage lithium cobaltate cathode active material can generally include doping type cobalt acid lithium from directly buying on the market
Matrix and the surface coating layer for being coated on doping type cobalt acid lithium matrix surface, wherein the doping vario-property of doping type cobalt acid lithium matrix is first
Element can be Mg, Al, Ti, Zr etc., and surface coating layer can be Co3(PO4)2、AlPO4、Mn3(PO4)2Equal phosphate or other substances.
The doped modification of cobalt acid lithium and surface cladding, form stable lattice, and the structure that cobalt acid lithium can be effectively suppressed in high-voltage state becomes
Change, hinder the Co oxidation electrolyte response inhabitation Co dissolution of surface high-valence state, thus cobalt acid lithium structure when can guarantee overcharge
Stability inhibits heat to generate.Also, in general, the cobalt acid lithium material that voltage state is higher, overcharge safety can be more excellent
It is different.
The negative electrode tab includes negative current collector and the negative electrode material layer on the negative current collector, the cathode material
The raw material of the bed of material includes negative electrode active material, cathode conductive agent and negative electrode binder, and the negative electrode active material includes interphase
Carbosphere graphite.
Artificial graphite is generally blocky or stratiform irregular structure, processes coating accumulation in collection liquid surface and is easy to produce sky
Gap causes contact area between graphite particle to become smaller, and electrode surface side reaction increases in charging process, is easy to produce structure tip heat
Amount accumulation causes heat that cannot dissipate in time.And the negative electrode active material of the application lithium ion battery uses carbonaceous mesophase spherules stone
Ink, be in chondritic, large bulk density, may be implemented it is tightly packed, when overcharging can avoid because irregular structure generate heat
Local accumulation；Specific surface area is small, electrolyte irreversible capacity caused by the side reactions such as Surface Creation SEI film when reducing charging
Loss improves security performance.
The diaphragm includes base membrane layer and the coat in the base membrane layer at least one side, the base membrane layer be PP,
Film layer made of PE, PP are successively folded, the coat are ceramic material layer.
Due to about 120~140 DEG C of PE diaphragm material fusing point, fusing point is lower sufficiently to be protected in inside battery thermal runaway
Positive/negative plate contact short circuit.Pure PP diaphragm fusing point is then 160 DEG C or so, but because being single layer structure, is easy to produce in process
Raw breaking point, it is big that secondary operation applies difficulty, and when battery thermal runaway correspond to breaking point and is easiest to lead to positive and negative anodes short circuit.The application
Lithium ion battery septation includes that tri- layers of basement membrane of PP, PE, PP are sequentially stacked the base membrane layer to be formed and the ceramics on base membrane layer
Material coat, wherein about 160 DEG C of PP/PE/PP material fusing point, material heat resistance is preferable, and the surface of base membrane layer carries out ceramic painting
Heat resistance can be further enhanced by covering, even if diaphragm melts, positive and negative anodes come into contact in a large area short circuit and add when ceramic layer prevents diaphragm from melting
It is causus out of control.Coat can specifically be coated in the single side of base membrane layer or base membrane layer on opposite dual coating；The thickness of base membrane layer
Degree is generally 10~20um, and the thickness of coat is generally 1~5um.
Preferably, the raw material of the positive electrode material layer is led including 90~98wt% positive electrode active materials, 1~5wt% anode
Electric agent and 1~5wt% positive electrode binder.
Preferably, the negative electrode material layer is oily cathode material layer.
Preferably, the raw material of the negative electrode material layer is led including 90~96wt% negative electrode active material, 1~5wt% cathode
Electric agent and 3~5wt% negative electrode binder.
Preferably, the positive conductive agent and/or the cathode conductive agent include superconductive carbon black, carbon nanotube, VGDF,
At least one of graphene, electrically conductive graphite.
Preferably, the positive bonding agent and/or the negative electrode binder are oiliness binder, and specific can be selected gathers inclined fluorine
At least one in ethylene (PVDF), terpolymer Kynoar-tetrafluoroethylene-ethylene copolymer [P (VDF-TFE-P)]
Kind.Wherein, negative electrode binder preferably uses Kynoar (PVDF), and negative due to 112~145 DEG C of PVDF heat distortion temperature
Pole collocation uses, and softens (expansion) when reaching heat distortion temperature when overcharging heat heating, reduces graphite contact point/contact area,
Increase the impedance of cathode internal polarization, hinders Li+It is embedded in speed, can accordingly reduce infinite approach as impedance increases overcharge current
0A, therefore heat generation can be lowered, inhibit thermal runaway.
Commercialized conventional electrolysis liquid can be selected in the electrolyte；Such as it can be selected and select LiPF6, dicyandiamide solution EC,
The multicomponent mixture of DEC, DMC etc..Copper foil can be used in plus plate current-collecting body and negative current collector, and thickness is generally 5~15um.It is described
Positive plate and the two-sided surface density of the negative electrode tab are generally 190~200mg/cm2。
The present invention also provides a kind of preparation methods of above-mentioned lithium ion battery, comprising the following steps:
It takes the dissolution of raw material of positive electrode material layer in solvent, anode sizing agent is made；The anode sizing agent is coated in anode
Collection liquid surface through drying, rolls, after film-making, and positive plate is made；
It takes the dissolution of raw material of negative electrode material layer in solvent, negative electrode slurry is made；The negative electrode slurry is coated in cathode
Collection liquid surface through drying, rolls, after film-making, and negative electrode tab is made；
By the positive plate, the negative electrode tab and membrane winding at core；
The core is packed into outer enclosure structure, injection electrolyte simultaneously seals, then carries out chemical conversion treatment, be made lithium from
Sub- battery.
Preferably, the solvent is oil-based solvent, specifically optional N-Methyl pyrrolidone solvent.
The method have the benefit that: the present invention provides a kind of lithium ion battery and preparation method thereof, the ion-conductance
Chi Zhong, using high pressure lithium cobaltate cathode active material as the active material of positive electrode material layer, stable lattice, battery is in overcharge
When, positive electrode can inhibit material because de- lithium is excessive and generate amount of heat because of the reinforcing of material lattice structure；During cathode uses
Between phase carbosphere graphite as its negative electrode active material, because of its structure feature, when overcharging can avoid heat local accumulation；And every
Film is sequentially stacked the base membrane layer to be formed using tri- layers of basement membrane of PP, PE, PP and the ceramic material coat on base membrane layer is constituted,
It is heat-resist, it can prevent diaphragm melting from leading to positive and negative short circuit.Lithium ion battery of the present invention can form collaboration by the above three and make
With, effectively can mutually inhibit battery at different ambient temperatures (such as 5 DEG C, 25 DEG C, 50 DEG C) 1C charging 10V overcharge conductance
The thermal runaway of the battery of cause prevents on fire, the explosion of battery；It can take into account heavy impact, thermal shock, short circuit, needle thorn, squeeze simultaneously
The destructive collision such as pressure is not on fire, does not explode, and security performance is high.
Detailed description of the invention
For the clearer technical solution illustrated in the embodiment of the present invention, will make below to required in embodiment description
Attached drawing briefly describes.
Fig. 1 is that different voltages state cobalt acid lithium in 4.6V overcharges heating comparison diagram；
Fig. 2, which is positive electrode binder different content, overcharges temperature rise comparison diagram with comparing battery 4.6V；
Fig. 3 is the material morphology figure of carbonaceous mesophase spherules graphite in embodiment 1.
Specific embodiment
Present invention will be further explained below with reference to specific examples.It should be understood that these embodiments are merely to illustrate the present invention
Rather than it limits the scope of the invention.In addition, it should also be understood that, after reading the content taught by the present invention, those skilled in the art
Member can make various changes or modifications the present invention, and such equivalent forms equally fall within the application the appended claims and limited
Range.
The thermal stability for testing each voltage state cobalt acid lithium is filled with firstly, crossing to different voltages state cobalt acid lithium in 4.6V.Test
Method: by the sample for having object phase change and the ginseng for not undergoing phase transition within the scope of institute's measuring temperature and being generated without any fuel factor
Than object, isothermal is carried out at identical conditions and is heated or cooled, when sample is undergone phase transition, is just produced between sample and reference substance
A raw temperature difference；One group of differential thermocouple being placed in below them generates thermoelectric force U Δ T, puts through differential thermal amplifier
Power compensation amplifier is sent into after big, the electric current of power compensation amplifier automatic adjustment compensation heater strip makes sample and reference substance
Between the temperature difference go to zero, the two temperature remains identical always, this heat compensation is the fuel factor of sample, in the form of electrical power show
It is shown on recorder.Specifically common 4.2V cobalt acid lithium, 4.35V high pressure cobalt acid lithium and 4.4V high pressure cobalt acid lithium are surveyed respectively
Examination, tests the ramp case that overcharges of each cobalt acid lithium, acquired results are as shown in Figure 1.As shown in Figure 1,4.35V high pressure cobalt acid lithium and
4.4V high pressure cobalt acid lithium is heated up after 4.6V is overcharged lower than common 4.2V cobalt acid lithium.It is more than 50% since conventional cobalt acid lithium takes off lithium
When will appear structural breakdown and discharge heat, probably begin to decompose for 138~197 DEG C.The application lithium ion battery is just
Pole active material uses high pressure lithium cobaltate cathode active material comprising doping type cobalt acid lithium matrix and is coated on doping type cobalt acid
The surface coating layer of lithium matrix surface is coated by doped modification and surface, and DSC fusing point is greater than 210 DEG C, and fusing point raising can
Overcharging property of promotion.
In addition, applicant uses different binder PVDF contents (including 1wt%, 3wt%, 5wt%) to battery at anode
It is tested in the influence that 4.6V overcharges underlaying surface temperature, acquired results are as shown in Figure 2.As shown in Figure 2, with binder PVDF
Content increases, and over-charging of battery surface temperature reduces.In addition, applicant is obtained by many experiments, the material of anode and cathode
Binder proportion is bigger in layer raw material proportioning, and over-charging is more excellent, but as consumption of binder increases, the electrical property of battery is such as
The performances such as multiplying power discharging, circulation, low temperature discharge can deteriorate therewith.Therefore, the application confirms that the raw material of positive electrode material layer includes 90
~98wt% positive electrode active materials, the agent of 1~5wt% positive conductive and 1~5wt% positive electrode binder；The raw material of negative electrode material layer
Including 90~96wt% negative electrode active material, 1~5wt% cathode conductive agent and 3~5wt% negative electrode binder, positive and negative pole material
Control can take into account lithium ion battery 10V over-charging and electrical property in the range.
Embodiment 1
It is viscous to weigh 96.8wt% positive electrode active materials 4.4V high voltage cobalt acid lithium, the super conductive black of 2wt%, 1.2wt%
Agent Kynoar is tied, solvent is made with N-Methyl pyrrolidone, slurry is made, using the aluminium foil of 12um thickness as collector, will be starched
Expect that dual coating is on aluminium foil and dry；Pole piece is rolled, positive plate, the two-sided surface density 408mg/cm of pole piece is made2.It will
94.5wt% carbonaceous mesophase spherules graphite (material morphology is as shown in Figure 3), the super conductive black of 1wt%, 3.5wt% binder are poly-
Vinylidene makees solvent with N-Methyl pyrrolidone, slurry is made, using the copper foil of 8um thickness as collector, by the two-sided painting of slurry
It overlays on copper foil and dry；Pole piece is rolled, negative electrode tab, the two-sided surface density 198mg/cm of pole piece is made2.Using PP/PE/PP tri-
Layer basement membrane is stacked to be constituted, with a thickness of the base membrane layer of 14um, and on base membrane layer two-sided mixed painting with a thickness of 3um ceramics glue material conduct
Coat constitutes diaphragm using as battery diaphragm.Electrolyte selects LiPF6, dicyandiamide solution EC, DEC, DMC's etc. is polynary mixed
Close object.It is put into battery case after positive plate, negative electrode tab and diaphragm are wound together, diaphragm is placed between positive/negative plate, is then infused
Enter electrolyte and seal, and carry out chemical conversion treatment, lithium ion battery is made.
Embodiment 2
The present embodiment difference from example 1 is that, positive raw material components are as follows: 98wt% positive electrode active materials
4.45V high voltage cobalt acid lithium, the super conductive black of 0.5wt%, 1.5wt% binder Kynoar, anode sizing agent single side apply
It overlays on plus plate current-collecting body；Cathode raw material components are as follows: 96wt% carbonaceous mesophase spherules graphite, the super conductive black of 0.5wt%,
3.5wt% binder Kynoar, negative electrode slurry single side are coated on negative current collector；The single side on PP/PE/PP base membrane layer
It is mixed to apply the obtained battery diaphragm of ceramic glue material.
Embodiment 3
The present embodiment difference from example 1 is that, positive raw material components are as follows: 90wt% positive electrode active materials
4.35V high voltage cobalt acid lithium, the super conductive black of 5wt%, 5wt% binder Kynoar, anode sizing agent single side are coated in
On plus plate current-collecting body；Cathode raw material components are as follows: 90wt% carbonaceous mesophase spherules graphite, the super conductive black of 5wt%, 5wt%
Binder Kynoar, negative electrode slurry dual coating is on negative current collector；Single side is mixed on PP/PE/PP base membrane layer applies pottery
Battery diaphragm is made in porcelain cement material.
Comparative example 1
The comparative example difference from example 1 is that, diaphragm use PE diaphragm or PP diaphragm or PP/PE/PP every
Film, pure membrane surface is without coating.
Comparative example 2
The comparative example difference from example 1 is that, cathode use conventional artificial's graphite and water prescription, tool
Body raw material components are as follows: 95.8wt% graphite, 1wt% carbon black, 1.4wt%SBR, 1.8wt%CMC.
Comparative example 3
The comparative example difference from example 1 is that, cathode use conventional artificial's graphite and water prescription (cathode
Formula is with comparative example 2), diaphragm uses PE diaphragm or PP diaphragm or PP/PE/PP diaphragm, and pure membrane surface is without coating.
Comparative example 4
The comparative example difference from example 1 is that, anode uses 4.2V routine cobalt acid lithium, and cathode uses normal
Advise artificial graphite and water prescription (cathode formula is with comparative example 2), diaphragm use PE diaphragm or PP diaphragm or PP/PE/PP every
Film, pure membrane surface is without coating.
Comparative example 5
The comparative example difference from example 1 is that, anode uses 4.2V routine cobalt acid lithium, and cathode uses normal
Advise artificial graphite and water prescription (cathode formula is with comparative example 2).
Comparative example 6
The comparative example difference from example 1 is that, anode use 4.2V routine cobalt acid lithium.
Comparative example 7
The comparative example difference from example 1 is that, cathode use artificial graphite oiliness formula；It specifically includes:
The super conductive black of 94.5wt% artificial graphite, 1wt%, 3.5wt% binder Kynoar.
Comparative example 8
The comparative example difference from example 1 is that, cathode use carbonaceous mesophase spherules graphite water-base formula, tool
Body includes: 95.8wt% carbonaceous mesophase spherules graphite, 1wt% carbon black, 1.4wt%SBR, 1.8wt%CMC.
The scheme of lithium ion battery obtained by above embodiments 1-3 and comparative example 1-8 is compared, table 1 specific as follows
It is shown.
The scheme comparison of lithium ion battery obtained by table 1 embodiment 1-3 and comparative example 1-8
Lithium ion battery obtained by above embodiments 1-3 and comparative example 1-8 is tested for the property, specific as follows:
(1) 25 DEG C, 1C/10V overcharge test
Lithium ion battery obtained by embodiment 1-3 and comparative example 1-8 takes 10 samples respectively, is tested as follows:
Battery under 25 ± 2 DEG C of states, charges to 10V with 1C electric current with 0.5C constant-current discharge to 3.0V., and then constant pressure 10V allows electric current
Decline is close to 0A, and monitoring battery temperature changes, and stops experiment after the 150min that charges.
Judgment criteria: not on fire, do not explode, then test passes through, and otherwise tests and does not pass through.
Acquired results are as shown in table 2:
25 DEG C of 2 lithium ion battery of table, 1C/10V overcharge test comparison
| Sample | Test percent of pass |
| Embodiment 1 | 10/10 |
| Embodiment 2 | 10/10 |
| Embodiment 3 | 10/10 |
| Comparative example 1 | 8/10 |
| Comparative example 2 | 0/10 |
| Comparative example 3 | 0/10 |
| Comparative example 4 | 0/10 |
| Comparative example 5 | 0/10 |
| Comparative example 6 | 7/10 |
| Comparative example 7 | 2/10 |
| Comparative example 8 | 0/10 |
(2) 5 DEG C, 1C/10V overcharge test
Lithium ion battery obtained by embodiment 1-3 and comparative example 1-8 takes 10 samples respectively, is tested as follows:
Battery shelves 4h under 5 ± 2 DEG C of states with 0.5C constant-current discharge to 3.0V., charges to 10V with 1C electric current, then constant pressure 10V allows
Electric current decline is close to 0A, and monitoring battery temperature changes, and stops experiment after the 150min that charges.
Judgment criteria: not on fire, do not explode, then test passes through, and otherwise tests and does not pass through.
Acquired results are as shown in table 3:
5 DEG C of 3 lithium ion battery of table, 1C/10V overcharge test comparison
(3) 50 DEG C, 1C/10V overcharge test
Lithium ion battery obtained by embodiment 1-3 and comparative example 1-8 takes 10 samples respectively, is tested as follows:
Battery shelves 4h under 50 ± 2 DEG C of states with 0.5C constant-current discharge to 3.0V., charges to 10V with 1C electric current, then constant pressure 10V
Electric current decline is allowed to be close to 0A, monitoring battery temperature changes, and stops experiment after the 150min that charges.
Judgment criteria: not on fire, do not explode, then test passes through, and otherwise tests and does not pass through.
Acquired results are as shown in table 4:
50 DEG C of 4 lithium ion battery of table, 1C/10V overcharge test comparison
| Sample | Test percent of pass |
| Embodiment 1 | 10/10 |
| Embodiment 2 | 10/10 |
| Embodiment 3 | 10/10 |
| Comparative example 1 | 8/10 |
| Comparative example 2 | 0/10 |
| Comparative example 3 | 0/10 |
| Comparative example 4 | 0/10 |
| Comparative example 5 | 0/10 |
| Comparative example 6 | 4/10 |
| Comparative example 7 | 0/10 |
| Comparative example 8 | 0/10 |
(4) 5 DEG C of charging thermal shock tests
Lithium ion battery obtained by embodiment 1-3 and comparative example 1-8 takes 10 samples respectively, is tested as follows:
At 5 DEG C of battery it is fully charged after, battery is placed in hot tank, and temperature rises to 130 DEG C ± 2 DEG C simultaneously with the rate of (5 DEG C ± 2 DEG C)/min
Keep the temperature 60min.
Judgment criteria: not on fire, do not explode, then test passes through, and otherwise tests and does not pass through.
Acquired results are as shown in table 5:
5 lithium ion battery of table, 5 DEG C of charging thermal shock test comparisons
(5) 5 DEG C of charging short-circuit tests
Lithium ion battery obtained by embodiment 1-3 and comparative example 1-8 takes 10 samples respectively, is tested as follows:
After battery is fully charged at 5 DEG C, battery is put into positive and negative with the conducting wire connection that internal resistance is 80 ± 20m Ω in 55 ± 5 DEG C of baking oven
Pole, occurs kindling or explosion or battery surface maximum temperature has dropped 20% and stops experiment.
Judgment criteria: not on fire, do not explode, then test passes through, and otherwise tests and does not pass through.
Acquired results are as shown in table 6:
6 lithium ion battery of table, 5 DEG C of charging short-circuit test comparisons
| Sample | Test percent of pass |
| Embodiment 1 | 10/10 |
| Embodiment 2 | 10/10 |
| Embodiment 3 | 10/10 |
| Comparative example 1 | 10/10 |
| Comparative example 2 | 7/10 |
| Comparative example 3 | 4/10 |
| Comparative example 4 | 3/10 |
| Comparative example 5 | 7/10 |
| Comparative example 6 | 10/10 |
| Comparative example 7 | 3/10 |
| Comparative example 8 | 10/10 |
By upper, lithium ion battery of the present invention can satisfy multinomial security performance test.As it can be seen that lithium ion battery of the present invention
Security performance is greatly improved, and is conducive to the market application prospect for improving lithium ion battery, has great production practices
Meaning.
Although specifically showing and describing the present invention in conjunction with preferred embodiment, those skilled in the art should be bright
It is white, it is not departing from the spirit and scope of the present invention defined by described claims, it in the form and details can be right
The present invention makes a variety of changes, and is protection scope of the present invention.
Claims (10)
1. a kind of lithium ion battery, which is characterized in that including positive plate, negative electrode tab, diaphragm, the diaphragm is set to the positive plate
Between the negative electrode tab；
The positive plate includes plus plate current-collecting body and the positive electrode material layer on the plus plate current-collecting body, the positive electrode material layer
Raw material include positive electrode active materials, positive conductive agent and positive electrode binder, the positive electrode active materials include lithium cobaltate cathode
Active material, the lithium cobaltate cathode active material are high voltage lithium cobaltate cathode active material；
The negative electrode tab includes negative current collector and the negative electrode material layer on the negative current collector, the negative electrode material layer
Raw material include negative electrode active material, cathode conductive agent and negative electrode binder, the negative electrode active material includes that mesocarbon is micro-
Ballstone ink；
The diaphragm includes base membrane layer and the coat in the base membrane layer at least one side, and the base membrane layer is PP, PE, PP
Film layer made of successively folding, the coat are ceramic material layer.
2. lithium ion battery according to claim 1, which is characterized in that the high voltage lithium cobaltate cathode active material is
High voltage lithium cobaltate cathode active material greater than 4.2V.
3. lithium ion battery according to claim 2, which is characterized in that the high pressure lithium cobaltate cathode active material is selected from
At least one of 4.35V, 4.4V, 4.45V, 4.5V high voltage lithium cobaltate cathode active material.
4. lithium ion battery according to any one of claim 1-3, which is characterized in that the raw material of the positive electrode material layer
Including 90~98wt% positive electrode active materials, the agent of 1~5wt% positive conductive and 1~5wt% positive electrode binder.
5. lithium ion battery according to any one of claim 1-3, which is characterized in that the negative electrode material layer is oiliness
Negative electrode material layer.
6. lithium ion battery according to claim 5, which is characterized in that the raw material of the negative electrode material layer include 90~
96wt% negative electrode active material, 1~5wt% cathode conductive agent and 3~5wt% negative electrode binder.
7. lithium ion battery described in -3 according to claim 1, which is characterized in that the positive conductive agent and/or described negative
Pole conductive agent includes at least one of superconductive carbon black, carbon nanotube, VGDF, graphene, electrically conductive graphite.
8. lithium ion battery described in -3 according to claim 1, which is characterized in that the anode bonding agent and/or described negative
Pole binder includes at least one of Kynoar, terpolymer Kynoar-tetrafluoroethylene-ethylene copolymer.
9. the preparation method of lithium ion battery of any of claims 1-8, which comprises the following steps:
It takes the dissolution of raw material of positive electrode material layer in solvent, anode sizing agent is made；The anode sizing agent is coated in anode collection
Body surface face through drying, is rolled, after film-making, and positive plate is made；
It takes the dissolution of raw material of negative electrode material layer in solvent, negative electrode slurry is made；The negative electrode slurry is coated in negative pole currect collecting
Body surface face through drying, is rolled, after film-making, and negative electrode tab is made；
By the positive plate, the negative electrode tab and membrane winding at core；
The core is packed into outer enclosure structure, electrolyte is injected and is sealed, then carries out chemical conversion treatment, lithium-ion electric is made
Pond.
10. the preparation method of lithium ion battery according to claim 9, which is characterized in that the solvent is N- methyl pyrrole
Pyrrolidone.
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