CN108461719A - It is a kind of richness lithium material/conductive organic polymer composite positive pole and electrode preparation method - Google Patents
It is a kind of richness lithium material/conductive organic polymer composite positive pole and electrode preparation method Download PDFInfo
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- CN108461719A CN108461719A CN201810063760.5A CN201810063760A CN108461719A CN 108461719 A CN108461719 A CN 108461719A CN 201810063760 A CN201810063760 A CN 201810063760A CN 108461719 A CN108461719 A CN 108461719A
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- 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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Abstract
The present invention relates to the preparation methods of a kind of rich lithium material/conductive organic polymer composite positive pole and electrode.The present invention first passes through a step oxalate co-precipitation solvent-thermal method and obtains the rodlike hierarchical structure lithium-rich anode material of Nano/micron；Then conductive cross-linked polymer coats lithium-rich anode material by the method for in-situ polymerization, obtains rich lithium material/conductive organic polymer composite positive pole.Prepared rich lithium material/conductive organic polymer composite positive pole can be used for preparing anode electrode.The present invention is by synthesizing the rodlike hierarchical structure lithium-rich oxide anode material of Nano/micron, so that material has the double dominant of nanometer and micrometer structure, lithium ion diffusion path is short, material structure stability is good, and conductive cross-linked polymer cladding also is carried out to the positive electrode, the electron transfer rate of rich lithium material is improved, reduces charge transfer resistance, cyclical stability is improved, the high rate performance of material is greatly improved.
Description
Technical field
The invention belongs to field of lithium ion battery, and in particular to a kind of richness lithium material/conductive organic polymer anode composite
The preparation method of material and electrode.
Background technology
Lithium ion battery alleviates dependence and increasingly serious ring of the people to fossil fuel as novel stored energy form
Border pressure.In recent years, stratiform lithium-rich manganese-based anode material xLi2MnO3·(1-x)LiMO2(the transition elements such as M=Co, Ni, Mn one
Kind or it is a variety of) since it is with high power capacity, low cost and environmental-friendly, electric vehicle and extensive energy storage power grid can be applied to
Field is known as one of most potential anode material for lithium-ion batteries of new generation.
Currently, or most of conducting polymer energy densities are low or power density is low.For example, poly- (to benzene) and poly-
Thiophene has quick charge-discharge performance, and charging and discharging multiplying power can be more than 10C or more, but their specific discharge capacity is relatively low,
In 50mAh/g or so；Polyaniline and polysulfide have a higher specific discharge capacity (being more than 150mAh/g), but these materials
High-rate charge-discharge capability is poor.Currently, polyaniline is already used to improve the chemical property of lithium-rich anode material, however it is conductive
Polyaniline thermal stability is poor, and high temperature easily decomposes, and conductivity is relatively low to be a problem to be solved always.And poly-triphenylamine
Poly- (to benzene) structure and high-energy density with high conductivity in the molecular structure of (Polytriphenylamine, PTPAn)
Aniline unit structure, and poly-triphenylamine comparison polyaniline have better thermal stability.Therefore there is high-energy density and height
The poly-triphenylamine of the electron transfer rate constant and good cavity transmission ability of power density and super large is great potential
Electrochemical material can greatly improve the high rate performance of rich lithium material by poly-triphenylamine in-situ polymerization on lithium-rich anode material.
But, it is desirable to the poly-triphenylamine of highly conductive ability is obtained, then must improve its degree of polymerization, and triphenylamine is as rigid radical,
Dissolubility can decline rapidly when the degree of polymerization improves, and be difficult to be dissolved into solvent again so as to cause the poly-triphenylamine of high polymeric form
In, seriously affect the ability that coating modification positive electrode is grown by in-situ precipitate.Meanwhile the unit price of triphenylamine monomer material is about
It it is 10 times of aniline, this largely influences cladding applications of the poly-triphenylamine on electrode material, hinders industrial-scale life
Production.Therefore the present invention provides a kind of with triphenylamine, and aniline is the conductive cross-linked polymer of Material synthesis, comprehensive triphenylamine and benzene
The advantages of both amine, improves the electrochemical stability and thermal stability of polymer.The conduction cross-linked polymer has network-like
Compliant conductive matrix skeleton has excellent electric charge transfer rate, thermal stability and cyclical stability.
Stratiform lithium-rich anode material can effectively release the limitation that positive low capacity " short slab " develops lithium ion battery, but
It is that there are still disadvantages for this kind of high performance positive electrode, i.e. ontology high rate performance is poor, cyclical stability difference etc..This also becomes it
The major obstacle and bottleneck promoted and applied in lithium ion battery.Being coated to rich lithium material can be from external times for improving material
Rate performance, is classified by using Nano/micron, then can improve chemical property from inside, this structure by nanometer small particles and
Micron grade matrix is constituted；Nano particle reduces the length of lithium ion diffusion, improves kinetics of diffusion, obtains relatively high capacity；
Micron particles ensure relatively low contact resistance, good structural stability and actual processing characteristic.Rodlike hierarchical structure richness lithium is just
Pole material has the double dominant of nanometer and micrometer structure, and lithium ion diffusion path is short, and material structure stability is good, to assign
The excellent high rate performance of lithium-rich anode material, structural stability and cycle performance.
Currently used conductive agent acetylene black during homogenate be easy reunite, be difficult to realize with lithium-rich anode material it
Between uniform mixing, cause the contact resistance of electrode very high, so as to cause capacitance loss.And by the way that conductive organic polymer is added
Composite material then can aid in the further dispersion of conductive agent acetylene black.Conductive organic polymer composite material not only has
The characteristics of high-energy density, high power density, and its fast charging and discharging conduction skeleton can be formed with conductive agent acetylene black and be cooperateed with
Effect, further increases the high rate performance of lithium-rich anode material.
Invention content
To solve the disadvantage that the prior art and shortcoming, the primary purpose of the present invention is that a kind of rich lithium material of offer/
The preparation method of conductive organic polymer composite positive pole.
Another object of the present invention is to provide rich lithium material/conductive organic polymer made from above-mentioned preparation method is compound
Positive electrode.
It is still another object of the present invention to provide above-mentioned rich lithium material/conductive organic polymer composite positive poles to prepare
Application in electrode.
The present invention also provides a kind of electricity prepared using above-mentioned rich lithium material/conductive organic polymer composite positive pole
Pole.
The object of the invention is achieved through the following technical solutions：
A kind of preparation method of richness lithium material/conductive organic polymer composite positive pole, the richness lithium material/conduction have
The chemical formula general formula of machine polymer composite anode material is：xLi2MnO3·(1-x)LiMO2；Wherein M is in transition metal layer
Metal ion, including Mn, Ni, Co, V, Sn, Mo, Al, Y's are one or more；X is for indicating molar ratio shared by corresponding component；Institute
It states x and meets 0 ＜ x ＜ 1；The preparation method is that a step oxalate co-precipitation-solvent-thermal method, includes the following steps：
The acetate of the lithium of required stoichiometry, the acetate of the M containing metal or nitrate are mixed in proportion, are dissolved in ethyl alcohol
In solution, mixed solution A is obtained；By excessive dissolving oxalic acid in ethanol solution, mixed solution B is obtained；By mixed solution A plus
Enter into mixed solution B, is transferred to water heating kettle after stirring a period of time, forerunner is made in 120~180 DEG C of 2~20h of hydro-thermal reaction
Body；After presoma is dried at 400~500 DEG C calcine 3~6h, then successively at 500~600 DEG C calcine 2~5h, 700~800 DEG C
2~5h, 800~900 DEG C of 12~20h of calcining are calcined, room temperature is quickly cooled to later and obtains the rodlike hierarchical structure of Nano/micron
Lithium-rich oxide anode material；
The rodlike hierarchical structure lithium-rich oxide anode material of Nano/micron is dissolved in conductive cross-linked polymer organic
In solvent at least one of (be preferably chloroform, dichloroethanes, benzene, toluene), lithium-rich anode material suspension is obtained；It should
4~12h is stirred by ultrasonic in suspension, makes conductive cross-linked polymer on lithium-rich anode material surface by evaporating solvent at normal temperatures
In-situ precipitate obtains the rodlike hierarchical structure lithium-rich anode material of Nano/micron of conductive cross-linked polymer cladding, i.e., the described rich lithium
Material/conductive organic polymer composite positive pole.
The organic solvent is preferably at least one of chloroform, dichloroethanes, benzene, toluene.
Preferably, the conductive cross-linked polymer is made by following steps：By triphenylamine and aniline with certain mol proportion
It is dissolved in organic solvent at least one of (be preferably chloroform, dichloroethanes, benzene, toluene), in the protection of inert gas
Under be stirred, while being slowly added to anhydrous ferric trichloride, controlling reaction temperature is reacted after 3~12h at 5~60 DEG C by product
It pours into excessive methanol, makes to have the conductive cross-linked polymer of reticular structure to precipitate；By product with methanol wash for several times,
It is stirred overnight in saturation ammonium hydroxide, is finally dried to obtain conductive cross-linked polymer.The drying is preferably dried in vacuo 12h at 60 DEG C.
It is furthermore preferred that in prepared by the conduction cross-linked polymer, triphenylamine account for triphenylamine and aniline integral molar quantity 0.4~
50%；The molar ratio of anhydrous ferric trichloride and polymer monomer (referring to triphenylamine and aniline) is 4:1.
Preferably, the mass concentration of the ethanol solution is 30~99.5%.
Preferably, during the cladding, conductive cross-linked polymer accounts for the rodlike hierarchical structure lithium-rich oxygen of Nano/micron
Compound positive electrode and the 3~30% of conductive cross-linked polymer gross mass.
Preferably, described be quickly cooled down can be one kind in furnace cooling, air cooling, liquid nitrogen cooling.
Preferably, it after mixed solution A being added to mixed solution B, is stirred 1~6 hour at 40~60 DEG C；It is described dry
It is dry refer to 60~80 DEG C vacuum drying 12~for 24 hours.During the effect of stirring is ageing so that particle fully connects with solution
It touches, it can be with homoepitaxial.
Above-mentioned richness lithium material/conductive organic polymer composite positive pole can be used for preparing electrode.
A kind of richness lithium material/conductive organic polymer composite positive pole anode composite, is prepared by following steps：
(1) preparation of conductive organic polymer composite material：Conductive organic polymer is subjected to ball milling mixing, obtains conduction
Organic polymer composite material；
(2) preparation of anode sizing agent：The rodlike hierarchical structure richness lithium material of Nano/micron that conductive cross-linked polymer is coated
As a positive electrode active material, claimed respectively with conductive agent acetylene black, conductive organic polymer composite material, binder PVDF
Amount；Then by the rodlike hierarchical structure lithium-rich anode of Nano/micron of the conductive agent acetylene black and conductive cross-linked polymer cladding
Composite material is thoroughly mixed uniformly, and bonding agent PVDF and conductive organic polymer composite wood are stirring evenly and then adding into dry-mixed
Material, it is dry-mixed stir evenly after add N-Methyl pyrrolidone formed slurry, control the solid content and slurry viscosity of slurry, obtain just
Pole slurry；
(3) preparation of anode electrode：Step (2) described anode sizing agent is coated on aluminium foil, is ground on milling roller
Pressure obtains lithium-rich anode material/conductive organic polymer composite material anode composite electrode after punching.
Preferably, the conductive organic polymer is by polyaniline, poly- to one in benzene, poly-triphenylamine, polypyrrole, polythiophene
Kind or several compositions.
Preferably, in the anode sizing agent, the rodlike hierarchical structure richness lithium material of Nano/micron of conductive cross-linked polymer cladding
Material, conductive organic polymer composite material, conductive agent acetylene black, the mass ratio of binder PVDF are as follows：Conductive cross-linked polymeric
The lithium-rich anode material of object cladding accounts for 70%~80%, conductive organic polymer composite material and accounts for 10%~20%, conductive agent second
Acetylene black accounts for 5%~20%, bonding agent PVDF and accounts for 5%~20%, and the sum of four degrees are 100%.
Preferably, the solid content in the anode sizing agent is 40~60%, and slurry viscosity is 4500~6000cps.
The present invention proposes rodlike point of the Nano/micron of conductive organic polymer composite material and conductive cross-linked polymer cladding
Application of composite of the level structure lithium-rich oxide anode material in anode electrode preparation, at the same propose using triphenylamine and
Cladding applications of the conductive cross-linked polymer that aniline is synthesized as polymerized monomer on lithium-rich manganese-based anode material, greatly improve richness
The high rate performance of lithium anode material, structural stability and cycle performance, to make the performance of lithium ion battery greatly be carried
It is high.
Compared with prior art, the present invention has the following advantages and beneficial effects：
(1) present invention is by synthesizing the rodlike hierarchical structure lithium-rich oxide anode material of Nano/micron so that material
Double dominant with nanometer and micrometer structure, lithium ion diffusion path is short, and material structure stability is good, to assign rich lithium just
The excellent high rate performance of pole material, structural stability and cycle performance.
(2) present invention to the rodlike hierarchical structure lithium-rich oxide anode material of Nano/micron by carrying out conductive friendship
Linked polymer coats, and improves the electron transfer rate of rich lithium material, reduces charge transfer resistance, improves cyclical stability, pole
The big high rate performance for improving material.
(3) present invention prepares electrode by the way that conductive organic polymer composite material is added, and solves single conductive agent acetylene
Black dispersion is uneven, the very high problem of the contact resistance of electrode, improves conductive capability, fast charging and discharging conduction skeleton can with lead
While electric agent acetylene black forms synergistic effect, polymer itself is also an electrode material, can effective deintercalate lithium ions, into
One step improves the chemical property of lithium-rich anode material.
Description of the drawings
Fig. 1 is the high rate performance test chart of embodiment 1,2,3 and comparative example 1.
Fig. 2 is the high rate performance test chart of embodiment 4,5,6 and comparative example 1.
Fig. 3 is the high rate performance test chart of embodiment 7,8 and comparative example 1.
Fig. 4 is the 2C cycle performance test charts of embodiment 1 and comparative example 2.
Fig. 5 is the high rate performance test chart of embodiment 1 and comparative example 3.
Fig. 6 is the 0.5Li that embodiment 1 provides2MnO3·0.5LiNi0.44Mn0.32Co0.24O2SEM figure.
The preparation of a kind of rich lithium material/conductive organic polymer composite positive pole and electrode that Fig. 7 is that embodiment 1 provides
Method flow diagram.
Specific implementation mode
With reference to embodiment and attached drawing, the present invention is described in further detail, but embodiments of the present invention are unlimited
In this.Room temperature and room temperature are 25 DEG C or so in embodiment experimental implementation.The percentage of ethanol solution is mass percent.
Embodiment 1
(1) preparation of lithium-rich anode material：
The lithium acetate of stoichiometric ratio, manganese acetate, cobalt acetate, nickel acetate are dissolved in 50% ethanol solution, gold is obtained
Belong to the mixed solution A that ion concentration is 2mol/L, by dissolving oxalic acid in 99.5% ethanol solution, obtaining concentration of oxalic acid is
2mol/L mixed solutions B.Mixed solution A is added drop-wise to dropwise in mixed solution B, after stirring 1 hour at 60 DEG C, is transferred to
Polytetrafluoroethylene (PTFE) water heating kettle, then reaction kettle sealing are placed in baking oven, 180 DEG C of isothermal reaction 12h, the lower 80 DEG C of dryings of presoma vacuum
12h, 450 DEG C of calcining 6h in Muffle furnace, then calcine 5h, 750 DEG C of calcinings under air atmosphere at 500 DEG C successively in tube furnace
2h, 900 DEG C of calcining 12h, liquid nitrogen quenching to room temperature obtain the rodlike hierarchical structure lithium-rich oxide anode material of Nano/micron
Expect 0.5Li2MnO3·0.5LiNi0.44Mn0.32Co0.24O2；Lithium-rich anode material 0.5Li2MnO3·
0.5LiNi0.44Mn0.32Co0.24O2SEM scheme as shown in fig. 6, it can be seen that the material be Nano/micron hierarchical structure, it is whole
Body structure is the hollow multi-pore micron stick that diameter is about 1um；And micron bar is by the irregular sheet of a diameter of 100~200nm
Grain composition.
By above-mentioned lithium-rich anode material with conductive cross-linked polymer with 90：10 mass ratio is dissolved in chloroform, is obtained rich
Lithium anode material suspension；12h is stirred by ultrasonic in the suspension, makes conductive cross-linked polymer by evaporating solvent at normal temperatures
It is precipitated in lithium-rich anode material surface in situ, obtains the rodlike hierarchical structure richness lithium of Nano/micron of conductive cross-linked polymer cladding
Positive electrode.
Wherein, the conductive cross-linked polymer is prepared according to the following steps：Triphenylamine, aniline is molten with certain mol proportion
Solution is stirred, while being slowly added to anhydrous ferric trichloride, controlling reaction temperature is 20 in chloroform under the protection of nitrogen
DEG C, product is poured into excessive methanol after reacting 4h, makes to have the conductive cross-linked polymer of reticular structure to precipitate.By product
It is washed for several times with methanol, is stirred overnight in being saturated ammonium hydroxide, being finally dried in vacuo 12h at 60 DEG C obtains conductive cross-linked polymer；
The crosslinking ratio of triphenylamine and aniline is：Triphenylamine accounts for the 1% of the two integral molar quantity.Anhydrous ferric trichloride and polymer monomer
Molar ratio is 4:1.
(2) preparation of conductive organic polymer composite material：
By polyaniline, poly-triphenylamine in mass ratio 1：1 ball milling mixing is uniform, has obtained conductive machine polymer composites.
(3) preparation of anode sizing agent：
The lithium-rich anode material that conductive cross-linked polymer is coated as a positive electrode active material, with conductive agent acetylene black, lead
Electric organic polymer composite material, binder PVDF are 70 in mass ratio:10:10:10 are weighed；Then by the conductive agent
Acetylene black, lithium-rich anode material are thoroughly mixed uniformly, and to be stirring evenly and then adding into bonding agent PVDF organic with conduction dry-mixed
Polymer composites, it is dry-mixed stir evenly after add N-Methyl pyrrolidone and form slurry, the solid content for controlling slurry is
40%, slurry viscosity 4500cps obtain anode sizing agent.
(4) preparation of anode electrode：
The anode sizing agent is coated on aluminium foil, is rolled on milling roller, after punching obtain lithium-rich anode material/
Conductive organic polymer composite material anode composite electrode.
Using above-mentioned electrode as anode, lithium metal uses 1.0mol/L LiPF as cathode, electrolyte6- EC+DMC (bodies
Product is than being 1:1) simulated battery, is assembled into the dry glove box full of argon gas.Shelve it is carried out after 12h 0.1C, 0.5C,
The high rate performance of 1C, 2C, 3C, 5C, 10C are tested and the test of 2C cycle performances.Test results are shown in figure 1 for high rate performance, 2C
Cycle performance test chart is as shown in Figure 4.
Embodiment 2
The preparation method of embodiment 2 is same as Example 1, differs only in the lithium acetate of stoichiometric ratio, manganese acetate,
Cobalt acetate, nickel acetate, which are dissolved in 70% ethanol solution, to be changed to be dissolved in 50% ethanol solution.High rate performance test result is such as
Shown in Fig. 1.
Embodiment 3
The preparation method of embodiment 3 is same as Example 1, differs only in and is crosslinked above-mentioned lithium-rich anode material with conductive
Polymer is with 90：10 mass ratio, which is dissolved in, to be changed in chloroform with 85:15 mass ratio is dissolved in chloroform.High rate performance is tested
The results are shown in Figure 1, compares sol-gal process, forthright with higher times using the method for the present invention synthesis lithium-rich anode material
Energy；Use 50% ethanol solution during prepared by lithium-rich anode material, lithium-rich anode material and conductive cross-linked polymer with
90：It is best that 10 mass ratio carries out in-stiu coating high rate performance.
Embodiment 4
(1) preparation of lithium-rich anode material：
The lithium acetate of stoichiometric ratio, manganese nitrate, cobalt nitrate, nickel nitrate, yttrium nitrate are dissolved in 50% ethanol solution,
It obtains the mixed solution A that concentration of metal ions is 2.5mol/L and it is dense to obtain oxalic acid by dissolving oxalic acid in 50% ethanol solution
Degree is 2.5mol/L mixed solutions B.Mixed solution A is added drop-wise to dropwise in mixed solution B, after stirring 1 hour at 60 DEG C,
It is transferred to polytetrafluoroethylene (PTFE) water heating kettle, then reaction kettle, which seals, is placed in baking oven, 180 DEG C of isothermal reaction 20h, 80 under presoma vacuum
DEG C dry 12h, 450 DEG C of calcining 6h in Muffle furnace, then calcined successively at 500 DEG C under air atmosphere in tube furnace 2h, 750 DEG C
2h, 900 DEG C of calcining 14h are calcined, liquid nitrogen quenching to room temperature is obtaining the rodlike hierarchical structure lithium-rich oxide of Nano/micron just
Pole material 0.5Li2MnO3·0.5LiNi0.44Mn0.30Co0.24Y0.02O2；
By above-mentioned lithium-rich anode material with conductive cross-linked polymer with 95：5 mass ratio is dissolved in chloroform, obtains rich lithium
Positive electrode suspension；6h is stirred by ultrasonic in the suspension, by evaporating solvent conductive cross-linked polymer is existed at normal temperatures
Lithium-rich anode material surface in situ precipitates, and is obtaining the rodlike hierarchical structure richness lithium of Nano/micron of conductive cross-linked polymer cladding just
Pole material.
Wherein, the conductive cross-linked polymer is prepared according to the following steps：Triphenylamine, aniline is molten with certain mol proportion
Solution is stirred, while being slowly added to anhydrous ferric trichloride, controlling reaction temperature is 30 in chloroform under the protection of nitrogen
DEG C, product is poured into excessive methanol after reacting 6h, makes to have the conductive cross-linked polymer of reticular structure to precipitate.By product
It is washed for several times with methanol, is stirred overnight in being saturated ammonium hydroxide, being finally dried in vacuo 12h at 60 DEG C obtains conductive cross-linked polymer；
The crosslinking ratio of triphenylamine and aniline is：Triphenylamine accounts for the 2% of the two integral molar quantity.Anhydrous ferric trichloride and polymer monomer
Molar ratio is 4:1.
(2) preparation of conductive organic polymer composite material：
By polyaniline, poly-triphenylamine, gather to benzene in mass ratio 1：1：1 ball milling mixing is uniform, and it is compound to obtain organic polymer
Material.
(3) preparation of anode sizing agent：
The lithium-rich anode material that conductive cross-linked polymer is coated as a positive electrode active material, with conductive agent acetylene black, lead
Electric organic polymer composite material, binder PVDF are 75 in mass ratio:5:10:10 are weighed；Then by the conductive agent
The lithium-rich anode material that acetylene black, conductive cross-linked polymer coat is thoroughly mixed uniformly, is stirring evenly and then adding into dry-mixed
Bonding agent PVDF and conductive organic polymer composite material, it is dry-mixed stir evenly after add N-Methyl pyrrolidone and form slurry
Material, the solid content for controlling slurry is 45%, and slurry viscosity 5500cps obtains anode sizing agent.
(4) preparation of anode electrode：
The anode sizing agent is coated on aluminium foil, is rolled on milling roller, after punching obtain lithium-rich anode material/
Conductive organic polymer composite material anode composite electrode.
Using above-mentioned electrode as anode, lithium metal uses 1.0mol/L LiPF as cathode, electrolyte6- EC+DMC (bodies
Product is than being 1:1) simulated battery, is assembled into the dry glove box full of argon gas.Shelve it is carried out after 12h 0.1C, 0.5C,
The high rate performance of 1C, 2C, 3C, 5C, 10C are tested.Test results are shown in figure 2 for high rate performance.
Embodiment 5
The preparation method of embodiment 5 is same as Example 4, differs only in polyaniline, poly-triphenylamine, gathers to benzene by matter
Measure ratio 1：1：1 ball milling mixing is uniformly changed to polyaniline, poly-triphenylamine in mass ratio 1:2 ball milling mixings are uniform.
Test results are shown in figure 1 for high rate performance.
Embodiment 6
The preparation method of embodiment 6 is same as Example 4, differs only in liquid nitrogen cooling being changed to furnace cooling.
Test results are shown in figure 2 for high rate performance, made using different proportion shared by different polymer and polymer
Standby organic polymer composite material, final high rate performance difference, meanwhile, it can be obviously improved again using liquid nitrogen quenching
Rate performance.
Embodiment 7
(1) preparation of lithium-rich anode material：
The lithium acetate of stoichiometric ratio, manganese acetate, cobalt acetate, nickel acetate are dissolved in 60% ethanol solution, gold is obtained
Belong to the mixed solution A that ion concentration is 3mol/L, by dissolving oxalic acid in 50% ethanol solution, obtaining concentration of oxalic acid is
3mol/L mixed solutions B.Mixed solution A is added drop-wise to dropwise in mixed solution B, after stirring 2 hours at 60 DEG C, is transferred to
Polytetrafluoroethylene (PTFE) water heating kettle, then reaction kettle sealing are placed in baking oven, 180 DEG C of isothermal reaction 18h, the lower 80 DEG C of dryings of presoma vacuum
12h, 450 DEG C of calcining 6h in Muffle furnace, then calcine 5h, 750 DEG C of calcinings under air atmosphere at 500 DEG C successively in tube furnace
2h, 900 DEG C of calcining 12h, liquid nitrogen quenching to room temperature obtain the rodlike hierarchical structure lithium-rich oxide anode material of Nano/micron
Expect 0.5Li2MnO3·0.5LiNi0.44Mn0.32Co0.24O2；
By above-mentioned lithium-rich anode material with conductive cross-linked polymer with 90：10 mass ratio is dissolved in chloroform, is obtained rich
Lithium anode material suspension；8h is stirred by ultrasonic in the suspension, makes conductive cross-linked polymer by evaporating solvent at normal temperatures
It is precipitated in lithium-rich anode material surface in situ, obtains the rodlike hierarchical structure richness lithium of Nano/micron of conductive cross-linked polymer cladding
Positive electrode.
Wherein, the conductive cross-linked polymer is prepared according to the following steps：Triphenylamine, aniline is molten with certain mol proportion
Solution is stirred, while being slowly added to anhydrous ferric trichloride, controlling reaction temperature is 60 in chloroform under the protection of nitrogen
DEG C, product is poured into excessive methanol solution after reacting 1h, makes to have the conductive cross-linked polymer of reticular structure to precipitate.It will
Product is washed for several times with methanol, is stirred overnight in being saturated ammonium hydroxide, and 12h is finally dried in vacuo at 60 DEG C obtains conductive cross-linked polymeric
Object；The crosslinking ratio of triphenylamine and aniline is：Triphenylamine accounts for the 5% of the two integral molar quantity.Anhydrous ferric trichloride and polymer list
The molar ratio of body is 4:1.
(2) preparation of conductive organic polymer composite material：
By polyaniline, poly-triphenylamine in mass ratio 1：1 ball milling mixing is uniform, has obtained conductive machine polymer composites.
(3) preparation of anode sizing agent：
The lithium-rich anode material that conductive cross-linked polymer is coated as a positive electrode active material, with conductive agent acetylene black, lead
Electric organic polymer composite material, binder PVDF are 70 in mass ratio:10:10:10 are weighed；Then by the conductive agent
The lithium-rich anode material that acetylene black, conductive cross-linked polymer coat is thoroughly mixed uniformly, is stirring evenly and then adding into dry-mixed
Bonding agent PVD and conductive organic polymer composite material, it is dry-mixed stir evenly after add N-Methyl pyrrolidone and form slurry,
The solid content for controlling slurry is 45%, and slurry viscosity 5000cps obtains anode sizing agent.
(4) preparation of anode electrode：
The anode sizing agent is coated on aluminium foil, is rolled on milling roller, after punching obtain lithium-rich anode material/
Conductive organic polymer composite material anode composite electrode.
Using above-mentioned electrode as anode, lithium metal uses 1.0mol/L LiPF as cathode, electrolyte6- EC+DMC (bodies
Product is than being 1:1) simulated battery, is assembled into the dry glove box full of argon gas.Shelve it is carried out after 12h 0.1C, 0.5C,
The high rate performance of 1C, 2C, 3C, 5C, 10C are tested.
Test results are shown in figure 3 for high rate performance.
Embodiment 8
The preparation method of embodiment 8 is same as Example 7, differs only in positive active material, with conductive agent acetylene
Black, conductive organic polymer composite material, binder PVDF are 70 in mass ratio:10:10:10, which carry out weighing, is changed to by 80:5:
5:10 are weighed.
Test results are shown in figure 3 for high rate performance.Anode sizing agent preparation in, positive active material, conductive agent acetylene black,
Conductive organic polymer composite material, the scale effect of binder PVDF its high rate performance, wherein positive active material and is led
Electric agent acetylene black, conductive organic polymer composite material, binder PVDF are 70 in mass ratio:10:10:10 carry out anode sizing agent
Processability it is preferable.
Comparative example 1
In order to compare reference, we prepare lithium-rich anode material using sol-gal process, and are prepared in anode sizing agent
Conductive organic polymer composite material is added without in journey, steps are as follows：
(1) it will be dissolved in deionized water according to the lithium acetate of required ratio, manganese acetate, nickel acetate and cobalt nitrate, use electricity
Magnetic stirrer is stirred and heated to it 80~90 DEG C and citric acid (n metal ions is added into solution by a certain percentage：N lemons
Acid=1:1.05) it, forms it into green colloidal sol, after reacting 10min, ammonium hydroxide is added and adjusts the pH value of above-mentioned solution to 7.0；One section
After time heating evaporation, solution, which is formed, has very strongly adherent green gel；By gel in vacuum drying chamber after drying,
6h is calcined at 500 DEG C, then 900 DEG C of calcining 12h, after furnace cooling, obtain stratiform lithium-rich manganese base material 0.5Li2MnO3·
0.5LiNi0.44Mn0.32Co0.24。
(2) as a positive electrode active material by above-mentioned stratiform lithium-rich manganese base material, it is pressed with conductive agent acetylene black, binder PVDF
Mass ratio is 80:10:10 are weighed；Then the conductive agent acetylene black, bonding agent PVDF, lithium-rich anode material are fully stirred
It mixes uniformly mixed, N-Methyl pyrrolidone is added after dry-mixed stir evenly and forms slurry, the solid content for controlling slurry is
40%, slurry viscosity 4500cps obtain anode sizing agent.
(3) anode sizing agent is coated on aluminium foil, is rolled on milling roller, rich lithium material is being obtained after punching just
Pole electrode.
Using above-mentioned electrode as anode, lithium metal uses 1.0mol/L LiPF as cathode, electrolyte6- EC+DMC (bodies
Product is than being 1:1) simulated battery, is assembled into the dry glove box full of argon gas.Shelve it is carried out after 12h 0.1C, 0.5C,
The high rate performance of 1C, 2C, 3C, 5C, 10C are tested.
Comparative example 2
In order to compare reference, the preparation method of comparative example 2 is same as Example 1, and differing only in will be poly- with conduction crosslinking
Conjunction object carries out cladding and is changed to be coated with polyaniline, includes the following steps：
(1) lithium acetate of stoichiometric ratio, manganese acetate, cobalt acetate, nickel acetate are dissolved in 70% ethanol solution, are obtained
Concentration of metal ions is the mixed solution A of 2mol/L, and by dissolving oxalic acid in 99.5% ethanol solution, obtaining concentration of oxalic acid is
2mol/L mixed solutions B.Mixed solution A is added drop-wise to dropwise in mixed solution B, after stirring 1 hour at 60 DEG C, is transferred to
Polytetrafluoroethylene (PTFE) water heating kettle, then reaction kettle sealing are placed in baking oven, 180 DEG C of isothermal reaction 12h, the lower 80 DEG C of dryings of presoma vacuum
12h, 450 DEG C of calcining 6h in Muffle furnace, then calcine 5h, 750 DEG C of calcinings under air atmosphere at 500 DEG C successively in tube furnace
2h, 900 DEG C of calcining 12h, liquid nitrogen quenching to room temperature obtain the rodlike hierarchical structure lithium-rich oxide anode material of Nano/micron
Expect 0.5Li2MnO3·0.5LiNi0.44Mn0.32Co0.24O2；
By above-mentioned lithium-rich anode material and polyaniline with 90：10 mass ratio is dissolved in chloroform, obtains lithium-rich anode material
Expect suspension；12h is stirred by ultrasonic in the suspension, makes polyaniline in lithium-rich anode material table by evaporating solvent at normal temperatures
Face in-situ precipitate obtains the rodlike hierarchical structure lithium-rich anode material of Nano/micron of polyaniline-coated.
(2) by polyaniline, poly-triphenylamine in mass ratio 1：1 ball milling mixing is uniform, has obtained conductive machine polymer composite
Material.
(3) as a positive electrode active material by the lithium-rich anode material of polyaniline-coated, organic with conductive agent acetylene black, conduction
Polymer composites, binder PVDF are 70 in mass ratio:10:10:10 are weighed；Then by the conductive agent acetylene
Black, lithium-rich anode material is thoroughly mixed uniformly, and bonding agent PVDF and electrically conducting organic polymer are stirring evenly and then adding into dry-mixed
Object composite material, it is dry-mixed stir evenly after add N-Methyl pyrrolidone formed slurry, control slurry solid content be 40%,
Slurry viscosity is 4500cps, obtains anode sizing agent.
(4) anode sizing agent is coated on aluminium foil, is rolled on milling roller, lithium-rich anode material is obtained after punching
Material/conductive organic polymer composite material anode composite electrode.
Using above-mentioned electrode as anode, lithium metal uses 1.0mol/L LiPF as cathode, electrolyte6- EC+DMC (bodies
Product is than being 1:1) simulated battery, is assembled into the dry glove box full of argon gas.2C cycle performances are carried out to it after shelving 12h
Test.2C cycle performances test chart is coated as shown in figure 4, after the charge and discharge of 40 circle left and right using polyaniline
Lithium-rich anode material has begun with apparent capacity and has declined, and conductive cross-linked polymer is used to carry out cladding and can be obviously improved it following
Ring stability, after 100 circle charge and discharge cycles, capacity is without apparent decay.
Comparative example 3
In order to compare reference, the preparation method of comparative example 3 is same as Example 1, differs only in anode sizing agent and prepared
It is added without conductive organic polymer composite material in journey, includes the following steps：
(1) lithium acetate of stoichiometric ratio, manganese acetate, cobalt acetate, nickel acetate are dissolved in 50% ethanol solution, are obtained
Concentration of metal ions is the mixed solution A of 2mol/L, and by dissolving oxalic acid in 99.5% ethanol solution, obtaining concentration of oxalic acid is
2mol/L mixed solutions B.Mixed solution A is added drop-wise to dropwise in mixed solution B, after stirring 1 hour at 60 DEG C, is transferred to
Polytetrafluoroethylene (PTFE) water heating kettle, then reaction kettle sealing are placed in baking oven, 180 DEG C of isothermal reaction 12h, the lower 80 DEG C of dryings of presoma vacuum
12h, 450 DEG C of calcining 6h in Muffle furnace, then calcine 5h, 750 DEG C of calcinings under air atmosphere at 500 DEG C successively in tube furnace
2h, 900 DEG C of calcining 12h, liquid nitrogen quenching to room temperature obtain the rodlike hierarchical structure lithium-rich oxide anode material of Nano/micron
Expect 0.5Li2MnO3·0.5LiNi0.44Mn0.32Co0.24O2；
By above-mentioned lithium-rich anode material with conductive cross-linked polymer with 90：10 mass ratio is dissolved in chloroform, is obtained rich
Lithium anode material suspension；12h is stirred by ultrasonic in the suspension, makes conductive cross-linked polymer by evaporating solvent at normal temperatures
It is precipitated in lithium-rich anode material surface in situ, obtains the rodlike hierarchical structure richness lithium of Nano/micron of conductive cross-linked polymer cladding
Positive electrode.
Wherein, the conductive cross-linked polymer is prepared according to the following steps：Triphenylamine, aniline is molten with certain mol proportion
Solution is stirred, while being slowly added to anhydrous ferric trichloride, controlling reaction temperature is 20 in chloroform under the protection of nitrogen
DEG C, product is poured into excessive methanol solution after reacting 4h, makes to have the conductive cross-linked polymer of reticular structure to precipitate.It will
Product is washed for several times with methanol, is stirred overnight in being saturated ammonium hydroxide, and 12h is finally dried in vacuo at 60 DEG C obtains conductive cross-linked polymeric
Object；The crosslinking ratio of triphenylamine and aniline is：Triphenylamine accounts for the 1% of the two integral molar quantity.Anhydrous ferric trichloride and polymer list
The molar ratio of body is 4:1.
(2) lithium-rich anode material for coating conductive cross-linked polymer as a positive electrode active material, with conductive agent acetylene black,
Binder PVDF is 80 in mass ratio:10:10 are weighed；Then the conductive agent acetylene black, lithium-rich anode material is abundant
Be uniformly mixed, bonding agent PVDF be stirring evenly and then adding into dry-mixed, it is dry-mixed stir evenly after add N- crassitudes
Ketone forms slurry, and the solid content for controlling slurry is 40%, and slurry viscosity 4500cps obtains anode sizing agent.
(3) anode sizing agent is coated on aluminium foil, is rolled on milling roller, lithium-rich anode electricity is obtained after punching
Pole.
Using above-mentioned electrode as anode, lithium metal uses 1.0mol/L LiPF as cathode, electrolyte6- EC+DMC (bodies
Product is than being 1:1) simulated battery, is assembled into the dry glove box full of argon gas.Shelve it is carried out after 12h 0.1C, 0.5C,
The high rate performance of 1C, 2C, 3C, 5C, 10C are tested and the test of 2C cycle performances.Test results are shown in figure 5 for high rate performance, with
It is added without conductive organic polymer composite material to compare, takes and conductive organic polymer composite material is added to prepare anode sizing agent
Higher high rate performance can be obtained.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, it is other it is any without departing from the spirit and principles of the present invention made by changes, modifications, substitutions, combinations, simplifications,
Equivalent substitute mode is should be, is included within the scope of the present invention.
Claims (10)
1. a kind of preparation method of richness lithium material/conductive organic polymer composite positive pole, the richness lithium material/conduction are organic
The chemical formula general formula of polymer composite anode material is：xLi2MnO3·(1-x)LiMO2；Wherein M is the gold in transition metal layer
Belong to ion, including Mn, Ni, Co, V, Sn, Mo, Al, Y's one or more, 0 ＜ x ＜ 1；It is characterized in that, preparation method includes
Following steps：
The acetate of the lithium of required stoichiometry, the acetate of the M containing metal or nitrate are mixed in proportion, are dissolved in ethanol solution
In, obtain mixed solution A；By excessive dissolving oxalic acid in ethanol solution, mixed solution B is obtained；Mixed solution A is added to
In mixed solution B, it is transferred to water heating kettle after stirring a period of time, presoma is made in 180 DEG C of 2~20h of hydro-thermal reaction；By forerunner
After soma is dry at 400~500 DEG C calcine 3~6h, then successively at 500~600 DEG C calcine 2~5h, 700~800 DEG C calcining 2~
5h, 800~900 DEG C of 12~20h of calcining, are cooled to room temperature obtain the rodlike hierarchical structure lithium-rich oxygen of Nano/micron later
Compound positive electrode；
The rodlike hierarchical structure lithium-rich oxide anode material of Nano/micron and conductive cross-linked polymer are dissolved in organic solvent
In, obtain lithium-rich anode material suspension；4~12h is stirred by ultrasonic in the suspension, to lead by evaporating solvent at normal temperatures
Electrical coupling polymer is precipitated in lithium-rich anode material surface in situ, and the Nano/micron for obtaining conductive cross-linked polymer cladding is rodlike
Hierarchical structure lithium-rich anode material.
2. a kind of preparation method of rich lithium material/conductive organic polymer composite positive pole according to claim 1,
It is characterized in that, the conduction cross-linked polymer is made by following steps：Triphenylamine and aniline are dissolved in certain mol proportion
In organic solvent, be stirred under the protection of inert gas, while anhydrous ferric trichloride is added, controlling reaction temperature 5~
60 DEG C, product is poured into excessive methanol after reacting 3~12h, makes to have the conductive cross-linked polymer of reticular structure to precipitate；
Product is washed for several times with methanol, is stirred overnight in being saturated ammonium hydroxide, is finally dried to obtain conductive cross-linked polymer.
3. a kind of preparation method of rich lithium material/conductive organic polymer composite positive pole according to claim 2,
It is characterized in that, the triphenylamine accounts for the 0.4~50% of triphenylamine and aniline integral molar quantity；Anhydrous ferric trichloride and polymer monomer
Molar ratio be 4:1.
4. a kind of preparation method of rich lithium material/conductive organic polymer composite positive pole according to claim 1,
It is characterized in that, the mass concentration of the ethanol solution is 30~99.5%；
During the cladding, conductive cross-linked polymer accounts for the rodlike hierarchical structure lithium-rich oxide anode material of Nano/micron
Material and the 3~30% of conductive cross-linked polymer gross mass.
5. a kind of preparation method of rich lithium material/conductive organic polymer composite positive pole according to claim 1,
It is characterized in that, the cooling can be one kind in furnace cooling, air cooling, liquid nitrogen cooling；Mixed solution A is added to mixing
After solution B, stirred 1~6 hour at 40~60 DEG C；The drying refer to 60~80 DEG C vacuum drying 12~for 24 hours.
6. a kind of richness lithium material/conductive organic polymer composite positive pole, which is characterized in that it is any by claim 1 to 5
A kind of preparation method of rich lithium material/conductive organic polymer composite positive pole described in is made.
7. rich lithium material/conductive organic polymer composite positive pole answering in preparing anode electrode described in claim 6
With.
8. a kind of richness lithium material/conductive organic polymer composite positive pole anode composite, which is characterized in that it passes through following step
Suddenly it is prepared：
(1) conductive organic polymer is subjected to ball milling mixing, obtains conductive organic polymer composite material；
(2) the rodlike hierarchical structure richness lithium material of Nano/micron coated conductive cross-linked polymer as a positive electrode active material, with
Conductive agent acetylene black, conductive organic polymer composite material, binder PVDF are weighed respectively；Then by the conductive agent second
The rodlike hierarchical structure lithium-rich anode composite material of Nano/micron of acetylene black and conductive cross-linked polymer cladding is thoroughly mixed
It is even, be stirring evenly and then adding into binder PVDF and conductive organic polymer composite material dry-mixed, it is dry-mixed stir evenly after again plus
Enter N-Methyl pyrrolidone and form slurry, controls the solid content and slurry viscosity of slurry, obtain anode sizing agent；
(3) step (2) described anode sizing agent is coated on aluminium foil, is rolled on milling roller, rich lithium is being obtained after punching just
Pole material/conductive organic polymer composite material anode composite electrode.
9. a kind of rich lithium material/conductive organic polymer composite positive pole anode composite according to claim 8, special
Sign is, the conductive organic polymer is by polyaniline, poly- to one or more of benzene, poly-triphenylamine, polypyrrole, polythiophene
Composition.
10. a kind of rich lithium material/conductive organic polymer composite positive pole anode composite according to claim 8,
It is characterized in that, in the anode sizing agent, the rodlike hierarchical structure richness lithium material of Nano/micron of conductive cross-linked polymer cladding is led
Electric organic polymer composite material, conductive agent acetylene black, the mass ratio of binder PVDF are as follows：Conductive cross-linked polymer cladding
Lithium-rich anode material account for 70%~80%, conductive organic polymer composite material and account for 10%~20%, conductive agent acetylene black and account for
5%~20%, bonding agent PVDF accounts for 5%~20%, and the sum of four degrees are 100%；
Solid content in the anode sizing agent is 40~60%, and slurry viscosity is 4500~6000cps.
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| CN109755553A (en) * | 2019-03-20 | 2019-05-14 | 北京航空航天大学 | A kind of magnesium lithium Dual-ion cell composite positive pole and its preparation method and application, battery system |
| CN110937641A (en) * | 2019-11-20 | 2020-03-31 | 哈尔滨工业大学（深圳） | Sn element doped cobalt-free manganese-based solid solution lithium ion battery anode material and preparation method thereof |
| CN112201791A (en) * | 2020-10-23 | 2021-01-08 | 江苏大学 | Method for improving ternary cathode material of lithium ion battery by oxygen-absorbing self-healing film |
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| CN113823794A (en) * | 2021-08-04 | 2021-12-21 | 北京泰和九思科技有限公司 | Method for modifying positive electrode material coated by organic metal framework based polymer electrolyte |
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| CN113860280A (en) * | 2021-09-24 | 2021-12-31 | 惠州亿纬锂能股份有限公司 | Lithium manganese iron phosphate cathode material and preparation method and application thereof |
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