CN108134066A - Lithium ion battery anode glue size and preparation method, lithium ion battery and preparation method - Google Patents
Lithium ion battery anode glue size and preparation method, lithium ion battery and preparation method Download PDFInfo
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- CN108134066A CN108134066A CN201711402851.9A CN201711402851A CN108134066A CN 108134066 A CN108134066 A CN 108134066A CN 201711402851 A CN201711402851 A CN 201711402851A CN 108134066 A CN108134066 A CN 108134066A
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- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- 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
- H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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- 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
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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- 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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Abstract
The present invention discloses a kind of lithium ion battery anode glue size, is related to battery technology field.The anode sizing agent consists of the following components in percentage by weight：90 95% active materials, 1 4% binding agent, 1 9% conductive agent, 30 50% solvents, the active material is cobalt acid lithium and LiMn2O4 and/or the mixture of nickle cobalt lithium manganate, and the mixture contains the LiMn2O4 and/or nickle cobalt lithium manganate of the cobalt acid lithium that weight percent is 10 90% and surplus；The binding agent is Kynoar, and the conductive agent includes one or more of carbon black, carbon nanotubes, graphene, Super P Li, and the solvent is N methyl pyrrolidones.The present invention using cobalt acid lithium with and/or nickle cobalt lithium manganate mixture as the active material for preparing lithium ion battery anode glue size, the lithium ion battery of preparation has excellent high-rate discharge ability, high current ignition performance is more preferable, and cycle life, storge quality are good, while manufactures at low cost.
Description
Technical field
The present invention relates to battery technology field more particularly to a kind of lithium ion battery anode glue size and preparation method thereof, packets
Include the lithium ion battery of the lithium ion battery anode glue size and the preparation method of lithium ion battery.
Background technology
With the development of New Energy Industry, at present in power battery field, lithium ion battery is as green, the new energy of environmental protection
Source battery has been increasingly appearing in people’s lives.Emergency starting power supply currently on the market is generally using cobalt acid
The lithium ion battery of lithium system, the lithium ion battery of this kind of cobalt acid lithium system has high-rate discharge ability excellent and energy density
The advantages that high, still, the lithium ion battery of this kind of cobalt acid lithium system in anode sizing agent due to using pure cobalt acid lithium as activity
Substance, there are it is of high cost the defects of, in turn result in very high using the cost of goods manufactured of the lithium ion battery of cobalt acid lithium system.So
And the market sale price of battery is gone on along low, material price is high always, and the selling pressure of battery product is big, leads to product very
Difficulty sells to go out.Therefore, it is a kind of with excellent high-rate discharge ability there is an urgent need for proposing, manufacturing lithium ion battery at low cost just
Pole slurry and preparation method thereof, while also be able to propose a kind of lithium ion battery and lithium with the lithium ion battery anode glue size
The preparation method of ion battery.
Invention content
(1) technical problems to be solved
In order to solve the above problem of the prior art, the present invention provides a kind of with excellent high-rate discharge ability, system
Lithium ion battery anode glue size at low cost and preparation method thereof is made, while is also provided a kind of with lithium ion cell positive slurry
The lithium ion battery of material and the preparation method of lithium ion battery.
(2) technical solution
In order to achieve the above object, the main technical schemes that the present invention uses include：
The present invention provides a kind of lithium ion battery anode glue size, and the anode sizing agent is by following components in percentage by weight group
Into：90-95% active materials, 1-4% binding agents, 1-9% conductive agents, 30-50% solvents, the active material for cobalt acid lithium with
The mixture of LiMn2O4 and/or nickle cobalt lithium manganate, it is the cobalt acid lithium of 10-90% and remaining that the mixture, which contains weight percent,
The LiMn2O4 and/or nickle cobalt lithium manganate of amount；The binding agent be Kynoar, the conductive agent include carbon black, carbon nanotubes,
One or more of graphene, Super P Li, the solvent are N-Methyl pyrrolidone.
According to the present invention, when the active material is the mixture of cobalt acid lithium and LiMn2O4, cobalt acid lithium and LiMn2O4
Weight ratio is 3:7.
According to the present invention, when the active material is the mixture of cobalt acid lithium and nickle cobalt lithium manganate, cobalt acid lithium and nickel cobalt
The weight ratio of LiMn2O4 is 1:1.
According to the present invention, when the active material includes nickle cobalt lithium manganate, mole of nickel, cobalt, manganese in nickle cobalt lithium manganate
Than being 1:1:1 or 5:2:3 or 5:3:2.
According to the present invention, the D50 grain sizes of the LiMn2O4 are 8-15 μm, and the D50 grain sizes of the nickle cobalt lithium manganate are 3-9 μ
m。
Meanwhile the present invention provides a kind of preparation method of lithium ion battery anode glue size, includes the following steps：
Step 1 weighs the N-Methyl pyrrolidone for accounting for solvent total weight 70% and the binding agent Kynoar of whole, stirs
It mixes to being uniformly mixed, obtains mixed liquor；
Step 2 weighs conductive agent and is added in the mixed liquor that step 1 obtains, and stirs to conductive agent even particulate dispersion
In mixed liquor；
Step 3 weighs and accounts for the mixed of the cobalt acid lithium of active material admixture total weight 50% and LiMn2O4 or nickle cobalt lithium manganate
Object is closed, and is added in the mixed liquor that step 2 finally obtains, is stirred to being uniformly mixed, is added the remaining active material that accounts for and mix
The cobalt acid lithium of object total weight 50% and LiMn2O4 or the mixture of nickle cobalt lithium manganate are closed, stirs to slurry and is uniformly dispersed；
Step 4, the remaining N-Methyl pyrrolidone for accounting for solvent total weight 30% of addition, the viscosity for debugging slurry are 6000
± 2000mpa.S, solid content are 62% ± 5%, obtain anode sizing agent.
According to the present invention, in step 1, rotation 45Hz, revolve round the sun 40Hz, vacuum degree≤- 0.08MPa, mixing time 2h-
2.5h；In step 2, rotation 45Hz, revolve round the sun 40Hz, vacuum degree≤- 0.08MPa, mixing time 2h-3h；In step 3,
After feeding for the first time, rotation 45Hz, revolve round the sun 40Hz, vacuum degree≤- 0.08MPa, mixing time 0.5h-1h；Second of charging
Afterwards, rotation 45Hz, revolve round the sun 40Hz, vacuum degree≤- 0.08MPa, mixing time 3h-4h.
The present invention also provides a kind of lithium ion battery, including above-mentioned lithium ion battery anode glue size.
Further, the present invention provides a kind of preparation method of lithium ion battery, will use above-mentioned lithium ion battery just
Cell size made from the preparation method of pole slurry carries out following handle：
The cell size is coated and is compacted with pole piece；Pole piece is die cut, lamination or is wound as battery core, battery core point welds
After lug, top side seal and vacuum bakeout are completed；Battery core after cooling will be toasted and carry out note electrolyte, after fluid injection is stood, changed
Into, pumping sealing and partial volume, obtain finished product battery core.
According to the present invention, the surface density of the pole piece is in 100-200g/cm2, pole piece compaction density 3.0-3.5g/cm3；
When noting electrolyte, according to every ampere-hour capacity fluid injection 4.0-7.0g.
(3) advantageous effect
The beneficial effects of the invention are as follows：
It is compared with existing using pure cobalt acid lithium as the active material for preparing lithium ion battery anode glue size, the present invention adopts
By the use of cobalt acid lithium with and/or nickle cobalt lithium manganate mixture as the active material for preparing lithium ion battery anode glue size, preparation
Lithium ion battery has excellent high-rate discharge ability, in the high current ignition performance of igniter (emergency starting field of power supplies)
More preferably, cycle life, storge quality are good, while the positive electrode cost of the present invention drops to 40% or so of pure cobalt acid lithium,
It manufactures at low cost.
Description of the drawings
Fig. 1 is discharge curve comparison diagram of the lithium ion battery in 40C of the offer of the embodiment of the present invention 1；
Fig. 2 is the lithium ion battery that provides of the embodiment of the present invention 1 to discharge 2S in 150C, shelves 30s, continuous discharge 3 times
The discharge curve of simulated automotive igniting, wherein, lighter curve is current-time curvel, and darker curve is volt-time curve；
Fig. 3 is that the lithium ion battery that the embodiment of the present invention 1 provides turns 0.05C charge cutoffs/shelve by 2C chargings 4.2V
30min/6C is discharged to the cyclic lifetime test results figure of 3.0V；
Fig. 4 is that the lithium ion battery that the embodiment of the present invention 2 provides is compared with discharge curve of the pure LCO systems battery in 35C
Figure；
Fig. 5 be embodiment 2 provide lithium ion battery 120C discharge 2S, shelve 30s, the simulation vapour that continuous discharge is 3 times
The discharge curve of vehicle igniting；
Fig. 6 is that the lithium ion battery that the embodiment of the present invention 3 provides is compared with discharge curve of the pure LCO systems battery in 35C
Figure；
Fig. 7 is the lithium ion battery that provides of the embodiment of the present invention 3 to discharge 2S in 120C, shelves 30s, continuous discharge 3 times
The discharge curve of simulated automotive igniting, wherein, lighter curve is current-time curvel, and darker curve is volt-time curve.
Specific embodiment
In order to preferably explain the present invention, in order to understand, below in conjunction with the accompanying drawings, by specific embodiment, to this hair
It is bright to be described in detail.
A kind of lithium ion battery anode glue size, the anode sizing agent consist of the following components in percentage by weight：90-95% lives
Property substance, 1-4% binding agents, 1-9% conductive agents, 30-50% solvents, active material is cobalt acid lithium (LCO) and LiMn2O4 (LMO)
And/or the mixture of nickle cobalt lithium manganate (NCM), mixture contain the LCO that weight percent the is 10-90% and LMO of surplus
And/or NCM.Binding agent is Kynoar (PVDF), and conductive agent is included in carbon black, carbon nanotubes, graphene, electrically conductive graphite
It is one or more of.CNT may be selected in carbon nanotubes, and CNT is carbon nanotubes conductive agent, mainly plays electric action, more common carbon black
The electric conductivity of conductive agent is more preferable.Conductive black can select Super P Li.Solvent is N-Methyl pyrrolidone (NMP).
Active material can be the mixture of LCO and LMO, it is preferred that the weight ratio of LCO and LMO is 3:7.Active material
Can be the mixture of LCO and NCM, it is preferred that the weight ratio of LCO and NCM is 1:1.Active material can also be LCO and LMO
With the mixture of NCM, wherein, when active material is the mixture of LCO and LMO, the weight ratio of LCO and LMO is 3:7.Work as work
Property substance when being the mixture of LCO and NCM, the weight ratio of LCO and NCM is 1:1.When active material includes NCM, nickel in NCM,
Cobalt, manganese molar ratio be 1:1:1 or 5:2:3 or 5:3:2.
In the present invention, it needs to ensure the selection short grained active material of high-specific surface area, to ensure the height of battery
Multiplying power discharging property.Specifically, the D50 grain sizes of LMO or NCM are small, D50 grain sizes are less than 15 μm, and the D50 grain sizes of LMO are 8-
15 μm, specific surface area is 0.3~1.0m2The D50 grain sizes of/g, NCM are 3-9 μm, and specific surface area is 0.4~3.0m2/ g, in this way, not
The excellent high-rate discharge ability of lithium ion battery can be only realized, in the high current point of igniter (emergency starting field of power supplies)
Fiery performance is more preferable, and cycle life, storge quality are good, moreover it is possible to substantially reduce manufacture cost.
Meanwhile the present invention provides a kind of preparation method of lithium ion battery anode glue size, includes the following steps：
Step 1 weighs the NMP for accounting for solvent total weight 70% and the binding agent PVDF of whole, stirs to being uniformly mixed, obtains
Mixed liquor；
Step 2 weighs conductive agent and is added in the mixed liquor that step 1 obtains, and stirs to conductive agent even particulate dispersion
In mixed liquor；
Step 3 weighs and accounts for the LCO and LMO of active material admixture total weight 50% or the mixture of NCM, and be added to
It in the mixed liquor that step 2 finally obtains, stirs to being uniformly mixed, adds and remaining account for active material admixture total weight 50%
LCO and LMO or NCM mixture, stir to slurry and be uniformly dispersed；
Step 4, the remaining NMP for accounting for solvent total weight 30% of addition, debug the viscosity of slurry for 6000 ±
2000mpa.S, solid content are 62% ± 5%, obtain anode sizing agent.
According to the present invention, in step 1, rotation 45Hz, revolve round the sun 40Hz, vacuum degree≤- 0.08MPa, mixing time 2h-
2.5h；In step 2, rotation 45Hz, revolve round the sun 40Hz, vacuum degree≤- 0.08MPa, mixing time 2h-3h；In step 3,
After feeding for the first time, rotation 45Hz, revolve round the sun 40Hz, vacuum degree≤- 0.08MPa, mixing time 0.5h-1h；Second of charging
Afterwards, rotation 45Hz, revolve round the sun 40Hz, vacuum degree≤- 0.08MPa, mixing time 3h-4h.Mixing speed in above steps
It is unrestricted with mixing time, it can realize and be uniformly mixed or be uniformly dispersed.
The present invention also provides a kind of lithium ion battery, including above-mentioned lithium ion battery anode glue size.
Further, the present invention provides a kind of preparation method of lithium ion battery, will use above-mentioned lithium ion battery just
Cell size made from the preparation method of pole slurry carries out following handle：
Cell size using coating machine is coated and is compacted with pole piece, the surface density of pole piece is in 100-200g/cm2, pole
Piece compacted density is 3.0-3.5g/cm3；It is die cut using die-cutting machine by the size of technique, then by the pole piece being die cut folded
Lamination is carried out on piece machine or up- coiler or is wound as battery core, battery core point enters glue shell after welding lug, completes top side seal, is then placed in
Vacuum oven, vacuum bakeout 24-48h at 80-120 DEG C；Battery core after cooling will be toasted and carry out note electrolyte, held according to every ampere-hour
Fluid injection 4.0-7.0g is measured, after fluid injection is stood, is melted into, is evacuated sealing and partial volume, obtain finished product battery core.
Lithium ion battery prepared by the present invention is compared for the battery of pure cobalt acid lithium system, has excellent high-multiplying power discharge
Performance, more preferable in the heavy-current discharge performance of igniter (emergency starting field of power supplies), cycle life, storge quality difference are not
Greatly, it while manufactures cost and substantially reduces.
Preferred embodiment is set forth below to illustrate the present invention.
Embodiment 1
The present embodiment proposes a kind of preparation method of preferred pulp of lithium ion battery, according to formula rate (each slurry
The mass ratio LCO of component:LMO:PVDF:CNT:Super P Li:NMP=28.5:66.5:2:1:2:55), the first step weighs
The NMP and whole binding agent PVDF of solvent total weight 70% are accounted for, is separately added into a mixing bowl, rotation 45Hz, revolve round the sun 40Hz, vacuum
Degree≤- 0.08MPa, stirring 2h obtain mixed liquor to being uniformly mixed；Second step weighs Li and CNT nanometers of conductive agent Super P
In carbon pipe dry powder (PVP of the weight containing 0.8% carbon nanotubes powder) and a mixing bowl of addition above, rotation 45Hz, revolve round the sun 40Hz, vacuum
Degree≤- 0.08MPa, stirring 3h until conductive agent even particulate dispersion in a solvent；Third walks, and weighs account for prescription quality hundred respectively
It is 10 μm to divide than LCO the and D50 grain sizes for 50%, specific surface area 0.62m2The LMO of/g is weighed and is accounted for active material admixture
The mixture of the LCO and LMO of total weight 50%, wherein, the molar ratio of LCO and LMO is 3 in mixture:7, active material is mixed
It closes object to be added in the mixed liquor of second step acquisition, rotation 45Hz, revolve round the sun 40Hz, vacuum degree≤- 0.08MPa, and stirring 0.5h is mixed
After closing uniformly, then the remaining LCO and LMO for accounting for prescription quality percentage 50% added, then rotation 45Hz, revolve round the sun 40Hz,
Vacuum degree≤- 0.08MPa, stirring 3.5h is until slurry is uniformly dispersed；4th step, the remaining solvent total weight 30% of accounting for of addition
NMP debugs the viscosity of slurry, and viscosity, solid content is made to meet the requirements after (viscosity 6750mpa.S, solid content 65%), is obtained
Anode sizing agent can go out cylinder coating；5th step, anode sizing agent are coated using coating machine, and the requirement of coating is the face of pole piece
Density is in 150g/cm2, pole piece compaction density 3.2g/cm3；6th step is die cut using die-cutting machine by the size of technique, then
The pole piece being die cut is subjected to lamination on laminating machine or up- coiler or is wound as battery core, battery core point enters glue shell after welding lug,
Top side seal is completed, is then placed in vacuum oven, vacuum bakeout 36h at 100 DEG C；7th step will toast battery core after cooling and carry out
Electrolyte is noted, according to every ampere-hour capacity fluid injection 6.1g, after fluid injection is stood, is melted into, is evacuated sealing and partial volume, obtain finished product electricity
Core.
It is had excellent performance using the battery core of this technique, and its cost of manufacture is very cheap.Electric discharge of the battery in 40C is made in it
It performance and discharges 2S in 150C, shelves 30s, the discharge performance of simulated automotive high current that continuous discharge is 3 times igniting is respectively such as Fig. 1
Shown in Fig. 2.
It will be seen from figure 1 that the lithium ion battery of the present embodiment manufacture has more compared to for pure cobalt acid lithium system battery
Excellent high-rate discharge ability, when being discharged with 40C, the discharge voltage plateau of the battery of the present embodiment is about 3570mV, and pure
The discharge voltage plateau of cobalt acid lithium system battery is about 3500mV.This may be determined by following aspect factor：In a first aspect, due to
Under the conditions of high-multiplying power discharge, electrochemical reaction is controlled by diffusion, and diffusion of the lithium ion in active material is reaction controlling step
Suddenly, because the D50 grain sizes of the LMO of the present embodiment addition are smaller and structure is more stable, the diffusion path of lithium ion is short, and polarization is small.The
Two aspects since LMO has three-dimensional tunnel structure, are conducive to the embedding de- of lithium ion, the diffuser efficiency of lithium ion is high；And pure cobalt acid
The cobalt acid lithium of lithium system battery has two-dimensional layered structure, and lithium ion is only capable of carrying out embedding de-, the diffuser efficiency of lithium ion in interlayer
It is low.The third aspect, in electrode design, design is also optimized in the compacted density of active material, according to LMO and LCO materials
The characteristic of granular size difference suitably reduces compacted density (3.0g/m3), the compacting for both having met LMO in this way in turn ensures LCO's
Compacting more excellent can ensure that active material porosity is higher on pole piece, makes the better Electolyte-absorptive of pole piece, effectively shortens lithium
Ion positive active material diffusion path and ensure the diffusion rate of lithium ion, the high current for being more advantageous to electrode is put
Electricity, meanwhile, also ensure the cycle life of battery.
Car emergency startup power supply, which is mainly used for the sparking of meeting an urgent need of one kind when the accumulator that automobile is configured cannot strike sparks, to be made
Product, since the automotive ignition time is generally in 0.2~0.5S, the sparking electric currents of different automobiles generally in 120A~400A,
It is usually most of all in 200A or so, therefore, the heavy-current discharge 2S of setting emergency starting battery, it is already possible to meet vapour well
Vehicle igniting requirement.
Figure it is seen that the lithium ion battery of the present embodiment manufacture has excellent high current ignition performance.With 150C
During electric discharge, the discharge voltage of the 1st igniting of battery simulated automotive of the present embodiment is 7.79V, and the discharge voltage of the 2nd igniting is
8.71V, the discharge voltage of the 3rd igniting is 8.98V.Its 1st time heavy-current discharge be also determined by three factors above
, the 2nd time, the heavy-current discharge voltage of the 3rd time can rise, mainly internal temperature of battery rises what is influenced, when battery passes through
First time discharge temp can rise to 35~45 DEG C, and the raising of temperature is more advantageous to inside battery reaction rate and diffusion rate
It is promoted, is more advantageous to being large current discharge, so cell discharge voltage rises significantly.
Fig. 3, which is battery made by the present embodiment, to be turned 0.05C charge cutoffs/shelve 30min/6C by 2C chargings 4.2V and is discharged to
The cyclic lifetime test results figure of 3.0V.From figure 3, it can be seen that the battery capacity conservation rate that 1000 weeks the present embodiment of cycle make
80%, much larger than 500 weeks cycle life batteries of existing market, with excellent cycle life.This key factor is in battery
The selection high-specific surface area of active material, in addition the design of pole piece surface density is in place, it ensure that the imbibition of battery core and protect liquid
Performance, so as to ensure that battery has good cycle life.
Embodiment 2
The present embodiment proposes a kind of preparation method of preferred pulp of lithium ion battery, according to formula rate (each slurry
The mass ratio LCO of component:NCM:PVDF:CNT:Super P Li：NMP=47.5:47.5:2:1:2:55), the first step weighs
The NMP and whole binding agent PVDF of solvent total weight 70% are accounted for, is separately added into a mixing bowl, rotation 45Hz, revolve round the sun 40Hz, vacuum
Degree≤- 0.08MPa, stirring 2.5h obtain mixed liquor to being uniformly mixed；Second step weighs conductive agent Super P Li and CNT and receives
In rice carbon pipe dry powder (PVP of the weight containing 0.8% carbon nanotubes powder) and a mixing bowl of addition above, rotation 45Hz, revolve round the sun 40Hz, very
Reciprocal of duty cycle≤- 0.08MPa, stirring 2h until conductive agent even particulate dispersion in a solvent；Third walks, and weighs account for prescription quality respectively
LCO the and D50 grain sizes that percentage is 50% are 6 μm, specific surface area 0.83m2The NCM of/g is weighed and is accounted for active material mixing
The mixture of the LMO and NCM of object total weight 50%, wherein, LCO and NCM (NCM 1 in mixture:1:1 type, nickel, cobalt, manganese
Molar ratio is 1:1:1) molar ratio is 1:1, active material admixture is added in the mixed liquor of second step acquisition, rotation
45Hz, revolve round the sun 40Hz, vacuum degree≤- 0.08MPa, and stirring 1h after mixing, then by remaining accounts for prescription quality percentage
50% LCO and NCM is added, then rotation 45Hz, and revolve round the sun 40Hz, vacuum degree≤- 0.08MPa, and stirring 4h is until slurry disperses
Uniformly；4th step with the remaining viscosity of NMP debugging slurries for accounting for solvent total weight 30%, makes viscosity, solid content meet the requirements
After (viscosity 5800mpa.S, solid content 62%), anode sizing agent is obtained, cylinder coating can be gone out.5th step, anode sizing agent are adopted
Be coated with coating machine, the requirement of coating for pole piece surface density in 160g/cm2, pole piece compaction density 3.35g/cm3；The
Six steps are die cut by the size of technique using die-cutting machine, then the pole piece being die cut are folded on laminating machine or up- coiler
Piece is wound as battery core, and battery core point, which welds, enters glue shell after lug, completes top side seal, is then placed in vacuum oven, vacuum at 80 DEG C
Toast 48h；7th step will toast battery core after cooling and carry out note electrolyte, and according to every ampere-hour capacity fluid injection 4.5g, fluid injection is stood
Afterwards, it is melted into, is evacuated sealing and partial volume, obtain finished product battery core.
It is had excellent performance using the battery core of this technique, and its cost of manufacture is very cheap.Electric discharge of the battery in 35C is made in it
It performance and discharges 2S in 120C, shelves 30s, the discharge performance of simulated automotive high current that continuous discharge is 3 times igniting is respectively such as Fig. 4
Shown in Fig. 5.
From fig. 4, it can be seen that the lithium ion battery of the present embodiment manufacture has more compared to for pure cobalt acid lithium system battery
Excellent high-rate discharge ability, when being discharged with 35C, the discharge voltage plateau of the battery of the present embodiment is about 3570mV, and pure
The discharge voltage plateau of cobalt acid lithium system battery is about 3500mV.This may be determined by two aspect factors：On the one hand, due in height
Under the conditions of multiplying power discharging, electrochemical reaction is controlled by diffusion, and diffusion of the lithium ion in active material is Reaction controlling step, because
The D50 grain sizes of the NCM of the present embodiment addition are small and structure is more stable, and the diffusion path of lithium ion is short, and polarization is small.On the other hand,
Since NCM has three-dimensional tunnel structure, be conducive to the embedding de- of lithium ion, the diffuser efficiency of lithium ion is high；And pure cobalt acid lithium system
The cobalt acid lithium of battery has a two-dimensional layered structure, and lithium ion is only capable of carrying out in interlayer embedding de-, and the diffuser efficiency of lithium ion is low.
From fig. 5, it can be seen that the lithium ion battery of the present embodiment manufacture also has excellent high current ignition performance.With
When 120C discharges, the discharge voltage of the 1st igniting of battery simulated automotive of the present embodiment is 7.47V, and the electric discharge of the 2nd igniting is electric
It presses as 8.37V, the discharge voltage of the 3rd igniting is 8.69V.Its 1st time heavy-current discharge be to be determined by two factors above
It is fixed, the 2nd time, the heavy-current discharge voltage of the 3rd time can rise, mainly battery temperature rises what is influenced, when temperature is higher, more
Be conducive to the promotion of cell reaction rate and diffusion rate, so being more advantageous to being large current discharge.
Embodiment 3
The present embodiment proposes a kind of preparation method of preferred pulp of lithium ion battery, according to formula rate (each slurry
The mass ratio LCO of component:NCM:LMO:PVDF:CNT:Super P Li:NMP=28.5:28.5:38:2:1:2:55), first
Step weighs the NMP for accounting for solvent total weight 70% and whole binding agent PVDF, is separately added into a mixing bowl, rotation 45Hz, revolution
40Hz, vacuum degree≤- 0.08MPa, stirring 2h is equal to mixing, and obtains mixed liquor；Second step, weigh conductive agent Super P Li and
In CNT carbon nanotubes dry method (0.8%PVP) and a mixing bowl of addition above, rotation 45Hz, revolve round the sun 40Hz, and vacuum degree≤-
0.08MPa, stirring 2.5h until conductive agent even particulate dispersion in a solvent；Third walks, and weighs account for prescription quality percentage respectively
Than the LCO for 50%, D50 grain sizes are 3.5 μm, specific surface area 1.2m2NCM the and D50 grain sizes of/g are 8 μm, specific surface area
For 0.56m2The LMO of/g weighs the mixture of LCO, NCM and LMO for accounting for active material admixture total weight 50%, wherein,
LCO, NCM (NCM 1 in mixture:1:1 type, nickel, cobalt, manganese molar ratio be 1:1:1) and the molar ratio of LMO is 3:3:4, it will
Active material admixture is added in the mixed liquor of second step acquisition, rotation 45Hz, and revolve round the sun 40Hz, and vacuum degree≤- 0.08MPa is stirred
It mixes 1h after mixing, then remaining LCO, NCM and LMO for accounting for prescription quality percentage 50% is added, then rotation 45Hz,
Revolve round the sun 40Hz, vacuum degree≤- 0.08MPa, and stirring 3h is until slurry is uniformly dispersed；4th step accounts for solvent total weight with remaining
The viscosity of 30% NMP debugging slurries, makes viscosity, solid content meet the requirements (viscosity 5800mpa.S, solid content 62%)
Afterwards, anode sizing agent is obtained, cylinder coating can be gone out.5th step, anode sizing agent are coated using coating machine, and the requirement of coating is pole
The surface density of piece is in 150g/cm2, pole piece compaction density 3.1g/cm3；6th step is carried out using die-cutting machine by the size of technique
Cross cutting, then the pole piece being die cut is subjected to lamination on laminating machine or up- coiler or is wound as battery core, after battery core point welds lug
Enter glue shell, complete top side seal, be then placed in vacuum oven, vacuum bakeout 48h at 80 DEG C；7th step will toast electricity after cooling
Core carries out note electrolyte, according to every ampere-hour capacity fluid injection 5.6g, after fluid injection is stood, is melted into, is evacuated sealing and partial volume, obtained
Finished product battery core.
It is had excellent performance using the battery core of this technique, and its cost of manufacture is very cheap.Electric discharge of the battery in 35C is made in it
It performance and discharges 2S in 120C, shelves 30s, the discharge performance of simulated automotive high current that continuous discharge is 3 times igniting is respectively such as Fig. 6
Shown in Fig. 7.
From fig. 6, it can be seen that the lithium ion battery of the present embodiment manufacture has more compared to for pure cobalt acid lithium system battery
Excellent high-rate discharge ability, when being discharged with 35C, the discharge voltage plateau of the battery of the present embodiment is about 3517mV, and pure
The discharge voltage plateau of cobalt acid lithium system battery is about 3505mV, and two curves essentially coincide.This may be determined by two aspect factors
It is fixed：On the one hand, since under the conditions of high-multiplying power discharge, electrochemical reaction is controlled by diffusion, expansion of the lithium ion in active material
It is Reaction controlling step to dissipate, and because the D50 grain sizes of the NCM and LMO of the present embodiment addition are small, grain structure is stablized, specific surface area
Greatly, it is uniform that attachment can be disperseed with conductive agent particle, and is added to carbon nanotubes conductive agent, tubular conductive channel can be more
The good diffusion path for building lithium ion, polarization are small.On the other hand, although NCM materials are poor with respect to high rate performance, pass through
Selection is more suitable for high-multiplying power discharge NCM materials, and such as 1:1:1 type NCM or 5:2:The NCM of 3 type monocrystalline type structures, to ensure that it can
Preferably to carry out multiplying power discharging.In addition, in electrode design, design, root is also optimized in the compacted density of active material
According to LMO and the characteristic of LCO material granule difference in size, compacted density (3.0g/m is suitably reduced3), both met the pressure of LMO in this way
The compacting of LCO is in turn ensured in fact, more excellent can ensure that active material porosity is higher on pole piece, makes pole piece preferably absorb electrolysis
Liquid effectively shortens lithium ion in the diffusion path of positive active material and the diffusion rate of guarantee lithium ion, more advantageous electricity
The electric discharge of the high current of pole, meanwhile, also ensure the cycle life of battery.
From figure 7 it can be seen that the lithium ion battery of the present embodiment manufacture has more compared to for pure cobalt acid lithium system battery
Excellent high current ignition performance.When being discharged with 120C, the discharge voltage of the 1st igniting of battery simulated automotive of the present embodiment is
7.95V, the discharge voltage of the 2nd igniting is 8.50V, and the discharge voltage of the 3rd igniting is 8.84V.
It is to be appreciated that it is described above to what specific embodiments of the present invention carried out simply to illustrate that the skill of the present invention
Art route and feature, its object is to allow those skilled in the art that can understand present disclosure and implement according to this, but
The present invention is not limited to above-mentioned particular implementations.Every various change made within the scope of the claims is repaiied
Decorations should all be covered within the scope of the present invention.
Claims (10)
1. a kind of lithium ion battery anode glue size, it is characterised in that：The anode sizing agent is by following components in percentage by weight group
Into：90-95% active materials, 1-4% binding agents, 1-9% conductive agents, 30-50% solvents, the active material for cobalt acid lithium with
The mixture of LiMn2O4 and/or nickle cobalt lithium manganate, it is the cobalt acid lithium of 10-90% and remaining that the mixture, which contains weight percent,
The LiMn2O4 and/or nickle cobalt lithium manganate of amount；The binding agent be Kynoar, the conductive agent include carbon black, carbon nanotubes,
One or more of graphene, Super P Li, the solvent are N-Methyl pyrrolidone.
2. lithium ion battery anode glue size according to claim 1, it is characterised in that：When the active material is cobalt acid lithium
During with the mixture of LiMn2O4, the weight ratio of cobalt acid lithium and LiMn2O4 is 3:7.
3. lithium ion battery anode glue size according to claim 1, it is characterised in that：When the active material is cobalt acid lithium
During with the mixture of nickle cobalt lithium manganate, the weight ratio of cobalt acid lithium and nickle cobalt lithium manganate is 1:1.
4. lithium ion battery anode glue size according to claim 1, it is characterised in that：When the active material includes nickel cobalt
During LiMn2O4, nickel in nickle cobalt lithium manganate, cobalt, manganese molar ratio be 1:1:1 or 5:2:3 or 5:3:2.
5. lithium ion battery anode glue size according to claim 1, it is characterised in that：The D50 grain sizes of the LiMn2O4 are
8-15 μm, the D50 grain sizes of the nickle cobalt lithium manganate are 3-9 μm.
6. according to the preparation method of claim 1-5 any one of them lithium ion battery anode glue sizes, it is characterised in that：Including
Following steps：
Step 1 weighs the N-Methyl pyrrolidone for accounting for solvent total weight 70% and the binding agent Kynoar of whole, and stirring is extremely
It is uniformly mixed, obtains mixed liquor；
Step 2 weighs conductive agent and is added in the mixed liquor that step 1 obtains, and stirs to conductive agent even particulate dispersion mixed
It closes in liquid；
Step 3, the mixture for weighing the cobalt acid lithium for accounting for active material admixture total weight 50% and LiMn2O4 or nickle cobalt lithium manganate,
And be added in the mixed liquor that step 2 finally obtains, it stirs to being uniformly mixed, adds that remaining to account for active material admixture total
The cobalt acid lithium of weight 50% and LiMn2O4 or the mixture of nickle cobalt lithium manganate, stir to slurry and are uniformly dispersed；
Step 4, the remaining N-Methyl pyrrolidone for accounting for solvent total weight 30% of addition, debug the viscosity of slurry for 6000 ±
2000mpa.S, solid content are 62% ± 5%, obtain anode sizing agent.
7. the preparation method of lithium ion battery anode glue size according to claim 6, it is characterised in that：In step 1, certainly
Turn 45Hz, revolve round the sun 40Hz, vacuum degree≤- 0.08MPa, mixing time 2h-2.5h；In step 2, rotation 45Hz, revolution
40Hz, vacuum degree≤- 0.08MPa, mixing time 2h-3h；In step 3, after feeding for the first time, rotation 45Hz, revolution
40Hz, vacuum degree≤- 0.08MPa, mixing time 0.5h-1h；After second feeds, rotation 45Hz, revolve round the sun 40Hz, vacuum degree
≤ -0.08MPa, mixing time 3h-4h.
8. a kind of lithium ion battery, it is characterised in that：It is starched including such as claim 1-5 any one of them lithium ion cell positive
Material.
9. a kind of preparation method of lithium ion battery, it is characterised in that：It will be using the lithium ion battery described in claim 6 or 7
Cell size made from the preparation method of anode sizing agent carries out following handle：
The cell size is coated and is compacted with pole piece；Pole piece is die cut, lamination or is wound as battery core, battery core point welds lug
Afterwards, top side seal and vacuum bakeout are completed；Battery core after cooling will be toasted and carry out note electrolyte, after fluid injection is stood, be melted into, taken out
Sealing gland mouth and partial volume, obtain finished product battery core.
10. the preparation method of lithium ion battery according to claim 9, it is characterised in that：The surface density of the pole piece exists
100-200g/cm2, pole piece compaction density 3.0-3.5g/cm3；When noting electrolyte, according to every ampere-hour capacity fluid injection 4.0-7.0g.
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