A kind of preparation method of lithium ion battery
Technical field:
The present invention relates to technical field of lithium ion battery electrode, and in particular to a kind of preparation method of lithium ion battery.
Background technique:
Lithium battery is one kind using lithium metal or lithium alloy as negative electrode material, using the one-shot battery of non-aqueous electrolytic solution,
It with lithium ion polymer battery is different with rechargeable battery lithium ion battery.The inventor of lithium battery is Edison.By
It is very active in the chemical characteristic of lithium metal, so that the processing of lithium metal, preservation, use, very high to environmental requirement.So
Lithium battery is not applied for a long time.With the development of twentieth century end microelectric technique, the equipment of miniaturization is increasing, right
Power supply proposes very high requirement.Lithium battery enters the large-scale practical stage therewith.The reaction of ferric phosphate lithium anode:Electric discharge
When lithium ion be embedded in, lithium ion deintercalation when charging.When charging:When LiFePO4 → Li1-xFePO4+xLi++xe- discharges:Li1-
XFePO4+xLi++xe- → LiFePO4 cathode, negative electrode material:Mostly use graphite.New research discovery titanate may be more preferable
Material.Negative reaction:Lithium ion is de- when electric discharge inserts, and lithium ion is inserted into when charging.When charging:XLi++xe-+6C → LixC6 is put
When electric:LixC6→xLi++xe-+6C.Ferric phosphate lithium cell has the characteristics that safety is good, energy density is higher, has become
Mainstream battery in power battery.However, institute is deviate from from positive electrode and migrated in the electrolytic solution to lithium ion under low temperature environment
The resistance being subject to increases, and the charge-discharge performance and cycle performance of ferric phosphate lithium cell drastically reduce, and therefore, improves LiFePO4 electricity
Pond charge-discharge performance at low ambient temperatures and cycle performance are of great significance.
Currently, the synthetic method of LiFePO 4 material is largely divided into solid phase method and liquid phase method.Solid phase method mainly utilizes iron
Salt, lithium salts and phosphate realize the synthesis of LiFePO4 in high temperature sintering.Liquid phase method is by soluble ferric iron salt, lithium salts and phosphoric acid
Salt dissolves in a solvent, LiFePO4 or its presoma is made using ionic reaction, then finished product is made by high temperature sintering.Solid phase
Method reaction is easy, and raw material is easily processed, and yield is high, but raw material pattern is not easily controlled, product tap density and compacted density
It is low.For example, patent of invention CN101200289, CN1762798, CN101140985 etc. are using process for solid phase synthesis route.
Some new synthetic methods, such as microwave process for synthesizing (CN101172597, CN101807692A), supersonic and co-deposition
(CN101800311A), it can sum up in the point that in solid-phase synthesis.And liquid phase method needs to carry out pre-processing using reaction kettle, together
When be also required to the processes such as dry, filtering, technics comparing is complicated.But product sphericity is generally preferable, tap density is higher, capacity
It is outstanding with high rate capability.Patent of invention CN101172599, CN101047242, CN101121509 are using process above
Route.The successful application of iron phosphate material is that its surface is coated with conductive carbon layer.Really a kind of lithium iron phosphate/carbon composite wood
Material.The LiFePO 4 material for only having coated carbon could normally play its chemical property.But the carbon that general technique is added
The bulk density of LiFePO 4 material is seriously reduced in loose distribution since quality is loose, and between lithium iron phosphate particles.It is negative
Pole material is one of critical material of lithium ion battery, and it is mainly charcoal class that the lithium ion battery negative material used is commercialized at present
Negative electrode material.It has height ratio capacity (200~400mAh/g), low electrode current potential (< 1.0V vs Li+/Li), high circulation effect
The advantages that rate (> 95%) and long circulation life.There are carbonaceous mesophase spherules (MCMB), graphite and nothing in charcoal class negative electrode material
Shape carbon, wherein graphite has good layer structure, reversible specific capacity is reachable because its good conductivity, crystallinity are high
300mah/g or more, Chen et al. have invented a kind of ultrafine graphite cathode material, the auxiliary material after using high-end graphite to produce for
The primary raw material of the product on the basis of making particle size reduction to 5um by attritioning, then is surface-treated, and is carbonized by 1200 °
Afterwards, then 3000 ° of graphitization sintering are carried out, then carries out coarse crushing sieving and acquires corresponding product, this product has good conductive work
With resistance is low, and processing performance is good in lithium ion battery production process, and performance is stablized, and it is rate lithium battery that cost performance is high
Best negative electrode material.But the disadvantage is that graphite material structural stability is poor, the poor compatibility with electrolyte, and Li ion has at it
Diffusion velocity in sequence layer structure is slow, and the material is caused to be unable to high rate charge-discharge.And soft carbon crystallinity is low, crystallite dimension
Small, interplanar distance is big, good with compatibility of electrolyte, but first charge-discharge irreversible capacity is preferable, and application range is smaller, to above
Some faults of construction of the artificial graphite as lithium ion battery negative material itself, in order to obtain the cathode material of high electrochemical performance
Material, it is necessary to the modification and modification on a deep step surface are carried out to it.
Summary of the invention:
The present invention overcomes the deficiencies of existing technologies, and provides a kind of preparation method of lithium ion battery.
The following technical solution is employed for the technical problems to be solved by the invention to realize:A kind of lithium ion battery preparation side
Method includes the following steps:
(1) prepared by positive plate:Prepare positive plate active material, and by positive plate active material, acetylene black and polyvinylidene fluoride
Alkene bonding agent and dehydrated alcohol are 80 according to weight percent:1:2:It at the uniform velocity stirs, obtains in 60 ratio investment reaction kettle
Anode sizing agent, and anode sizing agent is coated in aluminum foil current collector, cutting obtains positive plate;
(2) prepared by negative electrode tab:Negative electrode tab active material is prepared, and by negative electrode tab active material, the propylene of solid content 30%
Aqueous acid and acetylene black and dehydrated alcohol are 82 according to weight percent:1:1:It is at the uniform velocity stirred in 55 ratio investment reaction kettle
It mixes, obtains negative electrode slurry, and negative electrode slurry is coated in aluminum foil current collector, cutting obtains negative electrode tab;
(3) by positive plate and negative electrode tab and diaphragm zigzag lamination, tab welding, encapsulation, battery core baking, fluid injection, preliminary filling,
Drawing liquid molding prepares lithium ion battery, and wherein electrolyte is using addition sulfuric acid Asia ethylene rouge, fluorinated ethylene carbonate film forming addition
Agent electrolyte.
In the application, it is preferred that positive plate active material is through being prepared by the following steps in the step (1):
(4.1) by mass ratio 2:1 graphene and carbon nanotube are put into ethyl alcohol, and pass through the preliminary pulverization process of ultrasound
Afterwards, it is mixed 4~6 minutes, is then heated up in the environment of inert gas shielding with the speed of 2~4 DEG C/min at normal temperature
To 40~60 DEG C, then 4~6h is kept the temperature, then cooled to room temperature, obtains mixed solution;
The graphene is multi-layer graphene, and the inside of the multi-layer graphene is in 3 D stereo conductive network structure, institute
It states carbon nanotube to insert in the 3 D stereo conductive network, the grain diameter formed after multi-layer graphene and carbon nanotube effect
For 700nm~22um;
(4.2) LiFePO4 is crushed to 3~6um of partial size, and LiFePO4 is put into stirred tank, according to ferric phosphate
Mass ratio=1 of lithium and distilled water:2~7 ratio is slowly added distilled water, and adds coupling agent and acetylene black, quickly stirs
After 10~16min, the mixed solution in step (4.1) is added in stirred tank, is stirred evenly, obtains modified intermediate;
(4.3) the modification intermediate of step (4.2) preparation is added in atomizer and carries out spray drying treatment, during being somebody's turn to do
To be blown into gaseous carbon source under protective gas effect, make the gaseous carbon source modified intermediate surface crack to be formed it is amorphous
Carbon, the agraphitic carbon are coated on the surface of modified intermediate and form uniform clad;
(4.4) powder particle obtained in step (4.3) is acted in vacuum drying in 250~350 DEG C and protective gas
Lower calcining 3~4 hours, obtains positive plate active material.
In the application, it is preferred that the coupling agent is γ-mercaptopropyl trimethoxysilane, methyl isobutyl ketoxime base silicon
Alkane or vinyltriethoxysilane, the coupling agent:Acetylene black:The mass ratio of mixed solution is:(0.1~2:1~1.6:
100);
It is that will be modified intermediate to put into atomizer, and heat up in the state of nitrogen protection in the step (4.3)
Made annealing treatment to 500~700 DEG C, then by protective gas be loaded into 24~26% gaseous carbon source, gas flow rate 50~
1000ml/min, while atomizer is opened, protective gas takes the tiny ingredient being atomized in atomizer in high temperature furnace to, heat preservation 1
~12 hours, the gaseous carbon source is set to crack to form amorphous carbon in modified intermediate surface, which is coated on modification
The surface of intermediate simultaneously forms uniform clad, with a thickness of 0.3nm~30nm.
In the application, it is preferred that the negative electrode tab active material is through being prepared by the following steps:
(5) by mass ratio 2:1 graphene and carbon nanotube are put into dehydrated alcohol, and pass through the preliminary pulverization process of ultrasound
Afterwards, it is mixed 4~6 minutes, is then heated up in the environment of inert gas shielding with the speed of 2~4 DEG C/min at normal temperature
To 40~60 DEG C, then 4~6h is kept the temperature, then cooled to room temperature, obtains mixed solution;
The graphene is multi-layer graphene, and the inside of the multi-layer graphene is in 3 D stereo conductive network structure, institute
It states carbon nanotube to insert in the 3 D stereo conductive network, the grain diameter formed after multi-layer graphene and carbon nanotube effect
For 600nm~20um.
(6) it uses asphalt for base-material, which crush and ball-milling treatment to partial size is 120~140um, then
Will treated that particle puts into that processing is modified into reaction kettle, step includes:
(6.1) it uses flow velocity to be passed through nitrogen for 80~120 air speeds hourly, then carries out being warming up to 300~420 DEG C,
Heating rate is 40~60 DEG C/h, keeps the temperature 2~6h;
(6.2) pitch in part steps (6.1) is taken to be crushed to partial size in 20um hereinafter, and measure softening point, and herein
At a temperature of keep the temperature 4~6h, until the asphalt base-material of the softening point that measures at 180~380 DEG C;
(6.3) by the asphalt base-material cooled to room temperature in step (6.2), asphalt base-material, which is then crushed to partial size, is
18~20um, as modified pitch base-material;
(7) the sieve base-material of pitch obtained in step (6) is dissolved in the tetrahydrofuran solution that pitch is obtained in tetrahydrofuran,
And the tetrahydrofuran solution of the pitch of preparation is poured into mixed solution, stir 20~40min, obtain mixed slurry, then plus
Enter the solid masses percentage composition of solvent adjustment mixed slurry to 10~20%;
(8) mixed slurry in step (7) is dried by closed cycle spray drying machine, closed cycle spray is dry
The inlet temperature and outlet temperature of dry machine are respectively 120~140 DEG C and 70~60 DEG C, the atomizer of closed cycle spray drying machine
Revolving speed be 24000~26000r/min, obtain the negative electrode tab active material.
In the application, it is preferred that the weight of graphene in the step (5), the parts by weight of carbon nanotube and dehydrated alcohol
Measuring the ratio between number is 1:1~1:5.
In the application, it is preferred that the anode sizing agent is coated in 12 μ m-thick aluminum foil current collectors, coats two-sided surface density
500g/m2, to 160 μm of roller thickness, cutting obtains positive plate;The negative electrode slurry is coated in 6 μ m-thick copper foil current collectors, is applied
Cover two-sided face degree 230g/m2, to roller with a thickness of 150 μm;
The diaphragm uses 12 μ m-thick ceramic diaphragms, and the ceramic diaphragm is 9 μ m-thick polypropylene diaphragm single sides coating 3
μ m-thick Al2O3Ceramic coating.
Compared with prior art, the beneficial effects of the invention are as follows:
It 1, is by using carbon nanotube and graphene as modification when preparing positive plate active material in the application
Additive is formed including a kind of lithium iron phosphate positive material, and agraphitic carbon is coated on outer structure.On the one hand, graphene and carbon
The addition of nanotube is conducive to the activation of transition LiFePO4, and LiFePO4 can prevent graphene and carbon nanotube group
It is poly-, it is easier to obtain uniform and stable modified phosphate iron lithium, on the other hand, LiFePO4 will form rich lithium during discharge
Compound has good ionic conductivity, while the compound of these rich lithiums can repair the surface texture of lithium phosphate
Decorations, so that the electronic conductivity on phosphoric acid lithium surface improves;
2, in the application, when preparing positive plate active material, the clad is the agraphitic carbon of even compact, the nothing
Sizing carbon coating modified intermediate surface and form uniform clad, with a thickness of 0.3nm~30nm, this make its in addition to
Have outside the advantages of traditional clad, the ultra-thin clad of nanometer scale thickness, which also helps, reduces lithium ion in clad
Migration path further increases the high rate performance of material, makes it have good lithium ion conduction characteristic.
3, in the application, when preparing anode/negative electrode tab active material, the high conductance of graphene and carbon nanotube is utilized
Rate, the graphene are multi-layer graphene, and the inside of multi-layer graphene is in 3 D stereo conductive network structure, and then promotes lithium electricity
Migration velocity of the son in clad, carbon nanotube are inserted in the 3 D stereo conductive network, multi-layer graphene and carbon nanometer
The grain diameter formed after pipe effect is 700nm~22um, which is to be mixed 4~6 minutes at normal temperature, then lazy
40~60 DEG C are warming up to the speed of 2~4 DEG C/min in the environment of property gas shield, then keeps the temperature 4~6h, is then naturally cooled to
Room temperature obtains mixed solution, can further drain the micro-bubble between multi-layer graphene and carbon nanotubes in this way, is formed steady
Fixed binder course is conducive to the conductive characteristic for preferably playing graphene and carbon nanotube;
4, LiFePO 4 material surface is completely distributed in by technique provided by the present application, graphene and carbon nanotube,
The carbon layer on surface with high conductive capability is formd, loose bulk carbon-coating can't be generated, effectively increase LiFePO4
The bulk density and compacted density of positive electrode advantageously reduce lithium ion in the pole of positive electrode surface abjection and telescopiny
Change resistance;
5, the application is that carbon nanotubes and graphene are carried out moditied processing first when preparing negative electrode tab active material,
Using the high conductivity of graphene and carbon nanotube, graphene is multi-layer graphene, and the inside of multi-layer graphene is in 3 D stereo
Conductive network structure, and then migration velocity of the lithium electronics in clad is promoted, carbon nanotube is inserted conductive embedded in the 3 D stereo
In network, the grain diameter formed after multi-layer graphene and carbon nanotube effect is 700nm~22um, which is at normal temperature
It is mixed 4~6 minutes, is then warming up to 40~60 DEG C in the environment of inert gas shielding with the speed of 2~4 DEG C/min,
4~6h is kept the temperature again, then cooled to room temperature, obtain mixed solution, can further drain multi-layer graphene in this way and receive
Micro-bubble between rice carbon pipe, forms stable binder course, is conducive to the conduction for preferably playing graphene and carbon nanotube
Then characteristic prepares presoma using the dry mode of closed cycle spray, modified pitch it is evenly dispersed on the surface of graphene on,
After high-temperature heat treatment, one layer of unbodied charcoal is formed after asphalt carbonization, graphene surface is tightly wrapped in, forms one kind
The composite material of " core-shell " structure, the presence of clad not only reduce the specific surface area of material, prevent organic solvent
Into, achieve the purpose that obtain SEI film uniformly, fine and close, meanwhile, surface Carbon Materials are capable of fixing graphite flake, prevent graphite surface layer
Fall off so that the first charge discharge efficiency of material, specific capacity and cyclical stability obtain certain raising.
Specific embodiment:
In order to be easy to understand the technical means, the creative features, the aims and the efficiencies achieved by the present invention, tie below
Specific embodiment is closed, the present invention is further explained.
Embodiment 1:
A kind of preparation method of lithium ion battery, includes the following steps:
(1) prepared by positive plate:Prepare positive plate active material, and by positive plate active material, acetylene black and polyvinylidene fluoride
Alkene bonding agent and dehydrated alcohol are 80 according to weight percent:1:2:It at the uniform velocity stirs, obtains in 60 ratio investment reaction kettle
Anode sizing agent, and anode sizing agent is coated in aluminum foil current collector, cutting obtains positive plate;
(2) prepared by negative electrode tab:Negative electrode tab active material is prepared, and by negative electrode tab active material, the propylene of solid content 30%
Aqueous acid and acetylene black and dehydrated alcohol are 82 according to weight percent:1:1:It is at the uniform velocity stirred in 55 ratio investment reaction kettle
It mixes, obtains negative electrode slurry, and negative electrode slurry is coated in aluminum foil current collector, cutting obtains negative electrode tab;
(3) by positive plate and negative electrode tab and diaphragm zigzag lamination, tab welding, encapsulation, battery core baking, fluid injection, preliminary filling,
Drawing liquid molding prepares lithium ion battery, and wherein electrolyte is using addition sulfuric acid Asia ethylene rouge, fluorinated ethylene carbonate film forming addition
Agent electrolyte.
In the present embodiment.Positive plate active material is through being prepared by the following steps in the step (1):
(4.1) by mass ratio 2:1 graphene and carbon nanotube are put into ethyl alcohol, and pass through the preliminary pulverization process of ultrasound
Afterwards, it is mixed 4~6 minutes, is then heated up in the environment of inert gas shielding with the speed of 2~4 DEG C/min at normal temperature
To 40~60 DEG C, then 4~6h is kept the temperature, then cooled to room temperature, obtains mixed solution;
The graphene is multi-layer graphene, and the inside of the multi-layer graphene is in 3 D stereo conductive network structure, institute
It states carbon nanotube to insert in the 3 D stereo conductive network, the grain diameter formed after multi-layer graphene and carbon nanotube effect
For 700nm~22um;
(4.2) LiFePO4 is crushed to 3~6um of partial size, and LiFePO4 is put into stirred tank, according to ferric phosphate
Mass ratio=1 of lithium and distilled water:2~7 ratio is slowly added distilled water, and adds coupling agent and acetylene black, quickly stirs
After 10~16min, the mixed solution in step (4.1) is added in stirred tank, is stirred evenly, obtains modified intermediate;
(4.3) the modification intermediate of step (4.2) preparation is added in atomizer and carries out spray drying treatment, during being somebody's turn to do
To be blown into gaseous carbon source under protective gas effect, make the gaseous carbon source modified intermediate surface crack to be formed it is amorphous
Carbon, the agraphitic carbon are coated on the surface of modified intermediate and form uniform clad;
(4.4) powder particle obtained in step (4.3) is acted in vacuum drying in 250~350 DEG C and protective gas
Lower calcining 3~4 hours, obtains positive plate active material.
In the present embodiment, the coupling agent is γ-mercaptopropyl trimethoxysilane, methyl isobutyl ketoxime base silane or second
Alkenyl triethoxysilane, the coupling agent:Acetylene black:The mass ratio of mixed solution is:(0.1~2:1~1.6:100);
It is that will be modified intermediate to put into atomizer, and heat up in the state of nitrogen protection in the step (4.3)
Made annealing treatment to 500~700 DEG C, then by protective gas be loaded into 24~26% gaseous carbon source, gas flow rate 50~
1000ml/min, while atomizer is opened, protective gas takes the tiny ingredient being atomized in atomizer in high temperature furnace to, heat preservation 1
~12 hours, the gaseous carbon source is set to crack to form amorphous carbon in modified intermediate surface, which is coated on modification
The surface of intermediate simultaneously forms uniform clad, with a thickness of 0.3nm~30nm.
In the present embodiment, the negative electrode tab active material is through being prepared by the following steps:
(5) by mass ratio 2:1 graphene and carbon nanotube are put into dehydrated alcohol, and pass through the preliminary pulverization process of ultrasound
Afterwards, it is mixed 4~6 minutes, is then heated up in the environment of inert gas shielding with the speed of 2~4 DEG C/min at normal temperature
To 40~60 DEG C, then 4~6h is kept the temperature, then cooled to room temperature, obtains mixed solution;
The graphene is multi-layer graphene, and the inside of the multi-layer graphene is in 3 D stereo conductive network structure, institute
It states carbon nanotube to insert in the 3 D stereo conductive network, the grain diameter formed after multi-layer graphene and carbon nanotube effect
For 600nm~20um.
(6) it uses asphalt for base-material, which crush and ball-milling treatment to partial size is 120~140um, then
Will treated that particle puts into that processing is modified into reaction kettle, step includes:
(6.1) it uses flow velocity to be passed through nitrogen for 80~120 air speeds hourly, then carries out being warming up to 300~420 DEG C,
Heating rate is 40~60 DEG C/h, keeps the temperature 2~6h;
(6.2) pitch in part steps (6.1) is taken to be crushed to partial size in 20um hereinafter, and measure softening point, and herein
At a temperature of keep the temperature 4~6h, until the asphalt base-material of the softening point that measures at 180~380 DEG C;
(6.3) by the asphalt base-material cooled to room temperature in step (6.2), asphalt base-material, which is then crushed to partial size, is
18~20um, as modified pitch base-material;
(7) the sieve base-material of pitch obtained in step (6) is dissolved in the tetrahydrofuran solution that pitch is obtained in tetrahydrofuran,
And the tetrahydrofuran solution of the pitch of preparation is poured into mixed solution, stir 20~40min, obtain mixed slurry, then plus
Enter the solid masses percentage composition of solvent adjustment mixed slurry to 10~20%;
(8) mixed slurry in step (7) is dried by closed cycle spray drying machine, closed cycle spray is dry
The inlet temperature and outlet temperature of dry machine are respectively 120~140 DEG C and 70~60 DEG C, the atomizer of closed cycle spray drying machine
Revolving speed be 24000~26000r/min, obtain the negative electrode tab active material.
In the present embodiment, the parts by weight of graphene in the step (5), the parts by weight of carbon nanotube and dehydrated alcohol
The ratio between be 1:1~1:5.
In the present embodiment, the anode sizing agent is coated in 12 μ m-thick aluminum foil current collectors, coats two-sided surface density 500g/
m2, to 160 μm of roller thickness, cutting obtains positive plate;The negative electrode slurry is coated in 6 μ m-thick copper foil current collectors, and coating is double
Face face degree 230g/m2, to roller with a thickness of 150 μm;
The diaphragm uses 12 μ m-thick ceramic diaphragms, and the ceramic diaphragm is 9 μ m-thick polypropylene diaphragm single sides coating 3
μ m-thick Al2O3Ceramic coating.
Embodiment 2:
The present embodiment content and 1 content of embodiment are essentially identical, and something in common no longer repeats, the difference is that, this reality
It applies in example, when preparing positive plate active material, does not include step (4.3), modified intermediate is directly subjected to step (4.4),
Positive plate active material is obtained, and prepares and forms the lithium ion battery.
Embodiment 3:
The present embodiment content and 1 content of implementation are essentially identical, and something in common no longer repeats, the difference is that, this implementation
In example, when preparing positive plate active material, negative electrode tab active material, in step (4.1) and step (5), only by graphene
Mixing and pulverization process are carried out with carbon nanotube, obtains mixed solution, preparation forms the lithium ion battery.
Comparative example 1:
This comparative example uses and prepares to form the lithium-ion electric application No. is the technical solution in CN201710724700.9
Pond.
Battery performance test
Under conditions of same compacted density, by using the porosity of mercury injection apparatus measuring electrode, in dry gloves
Electrolyte is added dropwise in case and measures the sepage time, and to the lithium ion battery prepared in embodiment 1 to embodiment 3 and comparison 1 into
Row circulating battery and self discharge test, as a result such as the following table 1:
1 electrode physical property of table, chemical property comparing result
The above shows and describes the basic principles and main features of the present invention and the advantages of the present invention.The technology of the industry
Personnel are it should be appreciated that the present invention is not limited to the above embodiments, and the above embodiments and description only describe this
The principle of invention, without departing from the spirit and scope of the present invention, various changes and improvements may be made to the invention, these changes
Change and improvement all fall within the protetion scope of the claimed invention.The claimed scope of the invention by appended claims and its
Equivalent thereof.