CN109461912A - A kind of high performance lithium ion battery composite positive pole and preparation method thereof - Google Patents
A kind of high performance lithium ion battery composite positive pole and preparation method thereof Download PDFInfo
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Abstract
本发明公开了一种高性能锂离子电池复合正极材料及其制备方法，该正极材料包含：经聚偏氟乙烯预处理的镍基层状正极材料作为第一电极材料，及通过片状石墨烯完全包覆在第一电极材料上的橄榄石型正极材料，石墨烯占复合正极材料总质量的0.1%~0.5%；聚偏氟乙烯占复合正极材料质量的0.5%~2.0%；橄榄石型正极材料占复合正极材料总质量的5%~20%，余量均为镍基层状正极材料；镍基层状正极材料与橄榄石型正极材料的粒径比为50:1~300:1。镍基层状正极材料、橄榄石型正极材料和石墨烯三者之间形成导电网络，便于离子传输，且结构牢固，使得本发明的复合正极材料的放电容量高于任一组分材料，且相较于传统的镍基层状正极材料，其容量发挥、倍率性能、循环性能及安全性能均得到提高。
The invention discloses a high-performance lithium-ion battery composite positive electrode material and a preparation method thereof. The positive electrode material comprises: a nickel-based layer-like positive electrode material pretreated with polyvinylidene fluoride as a first electrode material, and a sheet-like graphene complete For the olivine-type positive electrode material coated on the first electrode material, graphene accounts for 0.1% to 0.5% of the total mass of the composite positive electrode material; polyvinylidene fluoride accounts for 0.5% to 2.0% of the mass of the composite positive electrode material; olivine-type positive electrode The material accounts for 5%~20% of the total mass of the composite cathode material, and the balance is nickel-based cathode material; the particle size ratio of the nickel-based cathode material and the olivine cathode material is 50:1~300:1. A conductive network is formed between the nickel-based positive electrode material, the olivine-type positive electrode material and the graphene, which is convenient for ion transport and has a firm structure, so that the discharge capacity of the composite positive electrode material of the present invention is higher than that of any component material, and the phase Compared with the traditional nickel-based cathode material, its capacity performance, rate performance, cycle performance and safety performance have been improved.
Description
Technical field
The present invention relates to a kind of high performance lithium ion battery composite positive poles and preparation method thereof.
Background technique
Since lithium ion battery has, high discharge voltage, high-energy-density, long circulation life, environmentally protective, self discharge is small, nothing
Outstanding advantages of memory effect, is widely used in mobile phone, laptop and other portable electronics, and gradually to big
The fields such as power system such as electric car, smart grid, satellite and distributed energy resource system are expanded.
The chemical property of lithium ion battery depends primarily on the structure and performance of electrode used therein material and electrolyte, especially
It is electrode material.The positive electrode for realizing commercialization at first is LiCoO2, still it is active in commercial market extensively now.But
LiCoO2Co element is toxic in positive electrode, and expensive scarcity of resources, thermodynamic stability is poor, in the use process of battery
There is the security risks that may be exploded, and seriously constrain LiCoO2The further development of positive electrode and large-scale commercial applications metaplasia
It produces and applies.
In LiCoO2Many replacement candidates materials in, Ni-based layered cathode material is because of its high capacity, low cost, of low pollution
And it is concerned by people, it is considered to be one of most promising positive electrode.However, the Ni-based stratiform of high nickel content is just
Pole material can generate the Ni with strong oxidizing property in the charge state4+, side reaction can occur with electrolyte and generate irreversible NiO
Phase causes structure change and capacity attenuation, and the heat and oxygen generated in the process can bring serious safety to battery
Hidden danger.
It is directed to Ni-based layered cathode material disadvantages mentioned above, current most important method of modifying is to carry out surface packet to it
It covering, barrier material itself is contacted with electrolyte and the direct of air, so that the cycle performance and security performance of material are improved, but this
The discharge capacity of kind of method of modifying often expendable material itself, and preparation method is relative complex, Ni-based layered cathode material
Feature easy to moisture absorption itself also brings difficulty to preparation process, is unfavorable for industrial scale production.
In recent years, the appearance of compound electrode material caused the extensive concern of researcher.So-called compound electrode
Just refer to that the electrode of two or more material composition, this compound electrode usually have not available for single type electrode
More superior performance.Two major classes can be divided by its composition, i.e., " electrode material+non-electrode material " type and " electrode material+
Electrode material " type." for electrode material+non-electrode material " type combination electrode: wherein non-electrode material rises in entire electrode
To booster action, such as material electric conductivity is improved, to promote chemical property.However " electrode material+electrode material " type is multiple
Composite electrode: its composition is electrode type material, its each composition can contribute capacity or energy for entire electrode.
High performance positive electrode is obtained, the positive electrode that both of which can be carried out lithium ion deintercalation reaction is matched
Mixed electrode is made as research hotspot in recent years.If component material is built into the composite wood with covering property structure
Material, so that it may the keeping body phase positive electrode intrinsic advantage performance while, the advantages of playing table phase material, and constitute between the two
Ion-electron way circulation frame often makes the performance of composite material better than the performance of any component.Existing coating technology substantially may be used
Two kinds are coated to be divided into liquid phase coating and solid phase.Traditional liquid phase method for coating grows another in a kind of component material surface in situ
The clad of even compact generally can be obtained in component material, but method is mostly complicated cumbersome, and generates pollution using solvent.It passes
Solid phase method for coating of uniting is simple, but the phenomenon that little particle spontaneous reunion often occurs, so that large particle surface cladding is uneven, thickness
It is different, have that part of the surface is exposed, and coat insecure, clad easily peels off during material slurry and pole piece roll-in etc..
Summary of the invention
The purpose of the present invention is overcoming the shortcomings of the prior art, a kind of high performance lithium ion battery anode composite is provided
Material and preparation method thereof, to improve discharge capacity, high rate performance, cycle performance and the safety of Ni-based layered cathode material
Energy.
In order to achieve the above object, the present invention provides a kind of high performance lithium ion battery composite positive poles, wherein should
Positive electrode includes: through the pretreated Ni-based layered cathode material of Kynoar as first electrode material, and passing through sheet
Graphene is coated on the second electrode material on first electrode material completely, which is olivine-type anode material
Material, wherein the graphene accounts for the 0.1% ~ 0.5% of composite positive pole gross mass；The Kynoar account for it is compound just
The 0.5% ~ 2.0% of pole quality of materials；The olivine-type positive electrode accounts for the 5% ~ 20% of composite positive pole gross mass, surplus
It is Ni-based layered cathode material；The partial size ratio of the Ni-based layered cathode material and olivine-type positive electrode be 50:1 ~
300:1。
Preferably, the Ni-based layered cathode material selection nickel cobalt lithium aluminate or nickle cobalt lithium manganate.
Preferably, appointing in the olivine-type positive electrode selection LiFePO4, lithium manganese phosphate and iron manganese phosphate for lithium
It anticipates one kind.
Preferably, the olivine-type positive electrode is dispersed in inside the interlayer of flake graphite alkene.
Preferably, the Kynoar is evenly distributed on Ni-based layered cathode material surface.
Preferably, the olivine-type positive electrode and graphene are coated on Ni-based layered cathode material surface completely.
Preferably, the olivine-type positive electrode is dispersed in inside the interlayer of flake graphite alkene as the first electricity
The surface coating layer of pole material.
Preferably, the surface coating layer with a thickness of 100 ~ 300nm.
Preferably, the partial size of the olivine-type positive electrode is 50 ~ 200nm.
Preferably, the molecular weight of the Kynoar is 100 ~ 1,300,000.
Preferably, the specific discharge capacity of the composite positive pole is simultaneously greater than any component material (first electrode material
Material, second electrode material) separately as anode material for lithium-ion batteries when specific discharge capacity.
The present invention also provides a kind of preparation methods of above-mentioned high performance lithium ion battery composite positive pole, wherein
The method includes:
Step 1, the graphene ethanol solution for preparing 0.1 ~ 1.0mg/mL, is added a certain amount of olivine-type material, and stirring 0.5 is small
Shi Hou ultrasonic disperse 2 hours, after being stirred for 0.5 hour, ultrasonic disperse 2 hours, is recycled 12 ~ 24 times；
Step 2, the solution filtering drying that ultrasonic disperse is good, obtains the composite material of graphene Yu olivine-type material；
Step 3, it by a certain amount of Ni-based layered cathode material and Kynoar, is put into mixing machine and stirs 4 ~ 6 hours, stir
Revolving speed is 1000rpm ~ 2000rpm；
Step 4, powder mixed in composite material obtained in step 2 and step 3 is put into planetary ball mill, is mixed
10 ~ 60min, rotational speed of ball-mill are 100rpm ~ 500rpm, finally obtain high performance composite positive pole.
High performance lithium ion battery composite positive pole provided by the invention and preparation method thereof has the advantage that
(1) olivine-type positive electrode is dispersed in inside the interlayer of flake graphite alkene by the first step by liquid phase method, is avoided with this
Nanoscale olivine-type positive electrode is reunited in subsequent ball milling mixed process；(2) second step is to Ni-based layered cathode material
Material particle is pre-processed, and Kynoar is wrapped up, and Ni-based layered cathode material large particle surface is made to have viscosity, is conducive to subsequent
The cladding of material simultaneously enhances binding force；(3) third step carries out dry mixed to the material that above-mentioned two step obtains, in the height of graphene
Under the collective effect of specific surface area and the high cohesive force on Ni-based layered cathode material surface, the shape on Ni-based layered cathode material surface
At even compact and firm nanometer clad.Have securely by composite positive pole obtained by the above method and what is penetrated through leads
Electric network can improve discharge capacity, the high rate performance, cycle performance of material simultaneously；And the nanometer clad on surface can inhibit pair
Reaction, improves the security performance of material.The Kynoar with cementation is contained in the composite positive pole and has had
The grapheme material of electric action can reduce the use content of binder and conductive agent in pole piece manufacturing process；Firm packet
Coating can also solve the problems, such as in the prior art in the slurry stage since density of material difference is easy segregation；Ni-based layered cathode material
Expect that surface alkalinty is big, easily absorb water, composite positive pole has fine and close clad, it can be stopped to contact with environment, and pole piece is raw
Requirement during production to drying shed dew point can reduce, and reduce the production cost of Ni-based layered cathode material system battery.Tradition
The clad of even compact generally can be obtained in liquid phase coating method, but method is mostly complicated cumbersome, and generates pollution using solvent.
Conventional solid method for coating is simple, but the phenomenon that little particle spontaneous reunion often occurs, so that large particle surface cladding is uneven, it is thick
It spends different, there is that part of the surface is exposed, and coat insecure, clad easily peels off during material slurry and pole piece roll-in etc..
Preparation method provided by the invention is simpler than Traditional liquid phase method for coating, pollution-free, and can evade and occur in conventional dry cladding
Large particle surface coat uneven incomplete defect, combine liquid phase coating and the advantages of solid phase coats, formed and uniformly caused
Close and firm nanometer clad also easily realizes large-scale serial production.
Detailed description of the invention
Fig. 1 is the scanning electron microscope (SEM) photograph of high performance lithium ion battery composite positive pole prepared by the embodiment of the present invention 1.
Fig. 2 is the transmission electron microscope picture of high performance lithium ion battery composite positive pole prepared by the embodiment of the present invention 1.
Fig. 3 is that all charge and discharge of head of high performance lithium ion battery composite positive pole prepared by the embodiment of the present invention 1 are bent
Line.
Fig. 4 is following at a temperature of 55 DEG C of high performance lithium ion battery composite positive pole prepared by the embodiment of the present invention 1
Ring performance curve.
Fig. 5 is the high rate performance curve of high performance lithium ion battery composite positive pole prepared by the embodiment of the present invention 2.
Fig. 6 is after high performance lithium ion battery composite positive pole initial charge prepared by the embodiment of the present invention 3 is complete
Differential thermal analysis (DSC) curve.
Specific embodiment
A specific embodiment of the invention is further described below in conjunction with attached drawing.
The present invention provides a kind of high performance lithium ion battery composite positive pole, the positive electrode include Ni-based stratiform just
Pole material, olivine-type positive electrode, graphene and Kynoar.
Kynoar is evenly distributed on Ni-based layered cathode material surface and constitutes first electrode material.
Olivine-type positive electrode is dispersed in inside the interlayer of flake graphite alkene, is coated on nickel completely as surface coating layer
Base layered cathode material surface.The surface coating layer with a thickness of 100 ~ 300nm.
Ni-based layered cathode material is any one in nickel cobalt lithium aluminate and nickle cobalt lithium manganate.
Olivine-type positive electrode selects in LiFePO4, lithium manganese phosphate and iron manganese phosphate for lithium as the second positive electrode
Any one.
The partial size of Ni-based layered cathode material and olivine-type positive electrode ratio is 50:1 ~ 300:1.
The partial size of olivine-type positive electrode is 50 ~ 200nm.
The molecular weight of Kynoar is 100 ~ 1,300,000.
Graphene accounts for the 0.1% ~ 0.5% of composite positive pole gross mass.
Olivine-type positive electrode accounts for the 5% ~ 20% of composite positive pole gross mass.
Kynoar accounts for the 0.5% ~ 2.0% of composite positive pole quality.
The specific discharge capacity of composite positive pole is simultaneously greater than any component material separately as lithium ion cell positive material
Specific discharge capacity when material.
The present invention also provides a kind of preparation methods of above-mentioned high performance lithium ion battery composite positive pole, wherein
The method includes:
Step 1, the graphene ethanol solution for preparing 0.1 ~ 1.0mg/mL, is added a certain amount of olivine-type material, and stirring 0.5 is small
Shi Hou ultrasonic disperse 2 hours, after being stirred for 0.5 hour, ultrasonic disperse 2 hours, is recycled 12 ~ 24 times；Step 2, by ultrasonic disperse
Good solution filtering drying, obtains the composite material of graphene Yu olivine-type material；Step 3, by a certain amount of Ni-based stratiform
Positive electrode and Kynoar are put into mixing machine and stir 4 ~ 6 hours, and speed of agitator is 1000rpm ~ 2000rpm；Step 4,
Powder mixed in composite material obtained in step 2 and step 3 is put into planetary ball mill, 10 ~ 60min is mixed,
Rotational speed of ball-mill is 100rpm ~ 500rpm, finally obtains high performance composite positive pole.
Embodiments of the present invention are described in detail by the following examples.
Embodiment 1
Step 1, the graphene ethanol solution 400mL of 0.5mg/mL is prepared, 10g LiFePO4 is added and surpasses after stirring 0.5 hour
Sound disperses 2 hours, after being stirred for 0.5 hour, ultrasonic disperse 2 hours, recycles 12 ~ 24 times；Step 2, by good molten of ultrasonic disperse
Liquid filtering drying obtains the composite material of graphene and LiFePO4；Step 3, the nickel cobalt lithium aluminate and 1.0g of 88.8g is poly- inclined
Vinyl fluoride is put into mixing machine and stirs 4 ~ 6 hours, and speed of agitator is 1000rpm ~ 2000rpm；Step 4, it will be obtained in step 2
Composite material and step 3 in mixed powder be put into planetary ball mill, mix 10 ~ 60min, rotational speed of ball-mill is
100rpm ~ 500rpm finally obtains high performance composite positive pole.
The SEM(scanning electron microscope of the composite positive pole obtained through this embodiment) figure as shown in Figure 1, A be graphene with
The composite material of LiFePO4, B are nickel cobalt aluminic acid lithium material, and C is high-performance composite positive pole.As can be seen from the figure phosphoric acid
The dispersion of iron lithium nano particle is present in the interlayer of graphene, in the high-specific surface area of graphene and the height on nickel cobalt lithium aluminate surface
Under the collective effect of cohesive force, the composite material of graphene and LiFePO4 is evenly coated at nickel cobalt lithium aluminate surface, is formed and is caused
Close clad realizes the complete cladding to nickel cobalt lithium aluminate.
The TEM(transmission electron microscope of the composite positive pole obtained through this embodiment) figure is as shown in Figure 2.It can from figure
Nickel cobalt lithium aluminate spheric granules surface does not have an exposed part out, surface there are one layer of fine and close clad, with a thickness of
200nm or so, thin and uniform, the phenomenon that not observing the spontaneous reunion of small lithium iron phosphate nano particle.Illustrate in final step
Ball milling mixing in small particles there is no reuniting, realize uniformly cladding, preparation method of the invention effectively compensates for existing packet
The deficiency of coating technique.
The all charging and discharging curves of the head of the composite positive pole obtained through this embodiment are as shown in figure 3, A is nickel cobalt lithium aluminate
Positive electrode, B are composite positive pole.Comparison is it can be found that there are ferric phosphates in the charging and discharging curve of composite positive pole
Lithium is located at the charging platform at 3.5 V and the discharge platform at 3.4 V, illustrates the nickel cobalt lithium aluminate in composite positive pole
Respective electrochemical characteristic has all been played with LiFePO4.Under 0.1 C multiplying power, the first circle of nickel cobalt aluminic acid lithium material, which discharges, to be held
Amount is 182.8 mAhg-1, and the discharge capacity of composite material has been increased to 202.5 mAhg-1, compared to nickel cobalt lithium aluminate
Material capacity improves 10.8 %.
Cycle performance curve of the composite positive pole obtained through this embodiment at a temperature of 55 DEG C as shown in figure 4, with
The electric current of 0.5 C carries out charge and discharge, and voltage range 2.8-4.3 V, A are nickel cobalt lithium aluminate cathode material, and B is anode composite material
Material.It can be seen from the figure that the discharge capacity for the first time of traditional nickel cobalt lithium aluminate cathode material is 174.8 mAh/g, recycle 100 weeks
Discharge capacity is 121.2 mAh/g afterwards, and capacity retention ratio is in 69.3 %；The discharge capacity for the first time of composite positive pole is 197.5
MAh/g, discharge capacity is 181.1 mAh/g after recycling 100 weeks, and capacity retention ratio reaches 91.7 %, and composite positive pole is in height
Cycle performance under temperature is obviously improved.For this explanation in composite positive pole, the cycle performance and heat of nickel cobalt lithium aluminate are steady
It is qualitative to be improved.
Embodiment 2
Step 1, the graphene ethanol solution 400mL of 0.5mg/mL is prepared, 10g LiFePO4 is added and surpasses after stirring 0.5 hour
Sound disperses 2 hours, after being stirred for 0.5 hour, ultrasonic disperse 2 hours, recycles 12 ~ 24 times；Step 2, by good molten of ultrasonic disperse
Liquid filtering drying obtains the composite material of graphene and LiFePO4；Step 3, the nickle cobalt lithium manganate of 88.8g and 1.0g is poly- inclined
Vinyl fluoride is put into mixing machine and stirs 4 ~ 6 hours, and speed of agitator is 1000rpm ~ 2000rpm；Step 4, it will be obtained in step 2
Composite material and step 3 in mixed powder be put into planetary ball mill, mix 10 ~ 60min, rotational speed of ball-mill is
100rpm ~ 500rpm finally obtains high performance composite positive pole.
The high rate performance curve of the composite positive pole obtained through this embodiment as shown in figure 5, A be nickle cobalt lithium manganate just
Pole material, B are composite positive pole.Reversible discharge specific capacity of the nickel-cobalt lithium manganate cathode material in 0.1 C is 159.6
mAh·g–1, reversible discharge specific capacity is 137.5 mAhg when 1 C–1, reversible discharge specific capacity is 117.5 mAhg when 3 C–1.Compared to nickel-cobalt lithium manganate material, composite positive pole either carries out charge and discharge under low range or high magnification, compound
Positive electrode all has higher specific discharge capacity.Wherein reversible discharge specific capacity when 0.1 C is 165.2 mAhg–1, 1 C
When reversible discharge specific capacity be 148.5 mAhg–1, reversible discharge specific capacity is 138.3 mAhg when 3 C–1.When electric discharge times
When rate returns to 0.1 C from 3 C, the reversible specific capacity of composite positive pole can be restored to 170.8 mAhg–1 , even higher than
It is that 0.1 C is tested for the first time as a result, capacity restoration rate be 103.4 %.And the capacity of nickel-cobalt lithium manganate material under the same conditions is extensive
Multiple rate is 95.4 %, and above data shows that composite positive pole high rate performance is excellent, compared to having for nickel-cobalt lithium manganate material
It is apparent to improve.This is primarily due to graphene with excellent electric conductivity, it can be achieved that the quick transmitting of electronics, can significantly drop
Low interfacial resistance improves the high rate performance of battery.The material when clad of compact and firm can also enhance big high-multiplying power discharge simultaneously
Structural stability.
Embodiment 3
Step 1, the graphene ethanol solution 400mL of 1.0mg/mL is prepared, 20g LiFePO4 is added and surpasses after stirring 0.5 hour
Sound disperses 2 hours, after being stirred for 0.5 hour, ultrasonic disperse 2 hours, recycles 12 ~ 24 times；Step 2, by good molten of ultrasonic disperse
Liquid filtering drying obtains the composite material of graphene and LiFePO4；Step 3, the nickel cobalt lithium aluminate and 0.8g of 78.8g is poly- inclined
Vinyl fluoride is put into mixing machine and stirs 4 ~ 6 hours, and speed of agitator is 1000rpm ~ 2000rpm；Step 4, it will be obtained in step 2
Composite material and step 3 in mixed powder be put into planetary ball mill, mix 10 ~ 60min, rotational speed of ball-mill is
100rpm ~ 500rpm finally obtains high performance composite positive pole.
Differential thermal point after all charging and discharging curve initial charges of the head of the composite positive pole obtained through this embodiment are complete
(DSC) curve is analysed as shown in fig. 6, A is nickel cobalt lithium aluminate cathode material, B is composite positive pole.As can be seen from the figure it mixes
The thermal decomposition temperature of positive electrode is higher than nickel cobalt lithium aluminate cathode material, improves the thermal stability of material.
High performance lithium ion battery composite positive pole provided by the invention and preparation method thereof, combine liquid phase coating with
The advantages of solid phase coats first effectively is dispersed olivine-type positive electrode by liquid phase method, secondly to Ni-based layered cathode material
Material particle is pre-processed, and finally the high cohesive force on the high-specific surface area of graphene and Ni-based layered cathode material surface is total to
Under same-action, only even compact and firm nanometer packet can be formed on Ni-based layered cathode material surface with dry ball milling mixing
Coating.This method is simpler than Traditional liquid phase method for coating, pollution-free, and can evade the bulky grain table occurred in conventional dry cladding
Bread covers uneven incomplete defect, also easily realizes large-scale serial production.Pass through anode composite material obtained by the above method
Material has grapheme material, constitutes securely and the conductive network of perforation, can improve simultaneously the discharge capacity of material, high rate performance,
Cycle performance；And the nanometer clad on surface can inhibit side reaction, improve the security performance of material.
In addition, in practical applications, Kynoar and tool with cementation have been contained in the composite positive pole
There is the grapheme material of electric action；The use content of binder and conductive agent can be reduced in pole piece manufacturing process, firmly
Clad can also solve the problems, such as in the prior art in the slurry stage since density of material difference is easy segregation；Ni-based layered cathode
Material surface alkalinity is big, easily absorbs water, and composite positive pole has fine and close clad, it can be stopped to contact with environment, pole piece
Requirement in production process to drying shed dew point can reduce, and reduce the production cost of Ni-based layered cathode material system battery.
It is discussed in detail although the contents of the present invention have passed through above preferred embodiment, but it should be appreciated that above-mentioned
Description is not considered as limitation of the present invention.After those skilled in the art have read above content, for of the invention
A variety of modifications and substitutions all will be apparent.Therefore, protection scope of the present invention should be limited to the appended claims.
Claims (9)
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| CN111509202A (en) * | 2020-04-16 | 2020-08-07 | 江西巴特威新能源科技有限公司 | Composite cathode material and preparation method and application thereof |
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