CN105576233B - A kind of Ni-based tertiary cathode material and preparation method thereof - Google Patents
A kind of Ni-based tertiary cathode material and preparation method thereof Download PDFInfo
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- CN105576233B CN105576233B CN201610120593.4A CN201610120593A CN105576233B CN 105576233 B CN105576233 B CN 105576233B CN 201610120593 A CN201610120593 A CN 201610120593A CN 105576233 B CN105576233 B CN 105576233B
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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Abstract
The present invention provides a kind of Ni-based tertiary cathode materials, are compounded in behind nickel-base material surface by coupling agent and are thermally treated resulting in again.The present invention passes through compound method of modifying, improve the hydrophilic surface nature of Ni-based tertiary cathode material, efficiently solve the problems, such as that Ni-based tertiary cathode material is more sensitive to Environmental Water, reduce the remaining lithium content of particle surface, and the loss of Ni-based tertiary cathode material specific discharge capacity will not be caused, and the dissolving of the particle surface transition metal ions in long-term cyclic process can be inhibited, corrosion of the HF generated in charge and discharge process to material surface is reduced, improves the chemical property of material.
Description
Technical field
The present invention relates to technical field of lithium ion, and in particular to a kind of Ni-based tertiary cathode material and its preparation side
Method.
Background technology
Lithium ion battery have operating voltage it is high, it is higher than energy, have extended cycle life, be light-weight, white few, the memoryless effect of discharging
Should be with cost performance ratio, oneself becomes the fields rechargeable type power supplys such as high power electric vehicle, artificial satellite, aerospace
Main selecting object.Therefore lithium ion battery and its associated materials become the research hotspot of scientific research personnel.Positive electrode is lithium
One of ion battery critical material decides the performance of lithium ion battery.And current limiting lithium ion power battery energy density,
The maximum bottleneck of power density, cycle life and security is positive electrode technology.
In current power lithium-ion battery positive electrode, the ternary layered positive electrode of nickle cobalt lithium manganate, chemical formula
For LiNi1-x-yCoxMnyO2, due to the synergistic effect of tri- kinds of elements of Ni, Co and Mn, have specific discharge capacity is high, energy density is high,
Cost is relatively low and advantages of environment protection, and it is great to become world market power lithium-ion battery application field increment in recent years
Positive electrode.Ni-based tertiary cathode material (LiNi among these1-x-yCoxMnyO2(1-x-y >=0.5)) combine LiCoO2,
LiNiO2And LiMnO2The advantages of three kinds of anode material for lithium-ion batteries, performance are better than any of the above one-component positive electrode,
There are apparent synergistic effects.In the system, the chemical property and physical property of material are with these three transition metal elements
The change of ratio and it is different.Ni is introduced, helps to improve the capacity of material, but Ni2+During too high levels, with Li+Mixing lead
Cycle performance is caused to deteriorate.By introducing Co, cation mixing occupy-place can be reduced, the layer structure of effective stabilizing material reduces
Impedance value improves electrical conductivity, but when Co ratios can cause a and c reductions and c/a increases, capacity when increasing to a certain range
It is lower.Mn is introduced, material cost can be not only reduced, but also the safety and stability of material can be improved.
But Ni-based tertiary cathode material is easily corroded in cyclic process there is also defect and causes cycle life drop
It is low, the chemical properties such as cycle performance and high rate performance are affected, so as to limit the large-scale commercialization of such material
Using；And since the nickel content of nickel-base material is high, when material exposes in air, easily occur with the moisture in air secondary
Reaction, causes that surface residual alkali content is higher, and main component is Li2CO3, in addition with a part with Li2SO4With the shape of LiOH
Formula exists, so Ni-based tertiary cathode material requires the moisture in strictly controlled environment in the production and packaging process,
The processing performance of material is seriously affected, so as to the yoke further developed as Ni-based tertiary cathode material.
Therefore, how to obtain one kind has better cycle performance and the Ni-based tertiary cathode material of high rate performance, simultaneously
The processability of Ni-based tertiary cathode material can also be promoted, it has also become field Nei Ge production firms urgent problem to be solved.
The content of the invention
In view of this, the present invention provides a kind of Ni-based tertiary cathode material and preparation method thereof, technical problems to be solved
It is the surface modified method of conventional Ni-based tertiary cathode material, the Ni-based tertiary cathode material that the present invention obtains has
Higher cycle performance and high rate performance, but also with preferable post-production performance.Meanwhile the preparation side that the present invention improves
Method is suitable for large-scale production and application, it is easy to accomplish homogenization and long term stabilization prepared by positive electrode batch.
The present invention provides a kind of Ni-based tertiary cathode materials, are compounded in by coupling agent behind nickel-base material surface and carry out heat again
Processing obtains.
Preferably, the coupling agent is the one or more of titanate coupling agent, aluminate coupling agent and silane coupling agent.
Preferably, shown in the chemical formula of the nickel-base material such as formula (I),
LiNi1-x-yCoxMnyO2(I)；Wherein, (1-x-y) >=0.5, x ＞ 0, y ＞ 0；
The mass ratio of the coupling agent and the nickel-base material is (0.005~0.1):1.
The present invention provides a kind of preparation methods of Ni-based tertiary cathode material, comprise the following steps：
1) by after nickel-base material presoma and lithium salts mixed calcining, nickel-base material is obtained；
Shown in the chemical formula of the nickel-base material such as formula (I),
LiNi1-x-yCoxMnyO2(I)；Wherein, (1-x-y) >=0.5, x ＞ 0, y ＞ 0；
2) above-mentioned steps are obtained nickel-base material and coupling agent to react in organic solvent, then it is fired after, obtain
Ni-based tertiary cathode material.
Preferably, the nickel-base material presoma is nickel cobalt manganese hydroxide, shown in chemical formula such as formula (II),
Ni1-x-yCoxMny(OH)2(II)；Wherein, (1-x-y) >=0.5, x ＞ 0, y ＞ 0.
Preferably, the lithium salts is the one or more in lithium carbonate, lithium hydroxide, lithium nitrate and lithium acetate；
The molar ratio of the nickel-base material presoma and the lithium salts is 1：(1.01~1.10).
Preferably, the temperature of the calcining is 700~1000 DEG C, and the time of the calcining is 4~20h.
Preferably, the organic solvent includes the one or more in ethyl alcohol, n-butanol, ethylene glycol, isopropanol and acetone；
The mass ratio of the nickel-base material and organic solvent is 1:(1~5).
Preferably, the temperature of the reaction is 50~90 DEG C, and the time of the reaction is 0.5~5h.
Preferably, the temperature of the roasting is 200~600 DEG C, and the time of the roasting is 1~5h.
The present invention provides a kind of Ni-based tertiary cathode materials, are compounded in by coupling agent behind nickel-base material surface and carry out heat again
Processing obtains, i.e., by being thermally treated resulting in again after coupling agent surface modification nickel-base material.Compared with prior art, the present invention is logical
The method of modifying of surface recombination is crossed, the hydrophilic surface nature of Ni-based tertiary cathode material is improved, efficiently solves Ni-based ternary
Positive electrode reduces the remaining lithium content of particle surface, and will not cause Ni-based to the more sensitive problem of Environmental Water
The loss of tertiary cathode material specific discharge capacity, and the particle surface transition metal ions in long-term cyclic process can be inhibited
Dissolving, reduce the corrosion of the HF that generates to material surface in charge and discharge process, improve the chemical property of material.
The specific volume the experimental results showed that lithium ion battery of Ni-based tertiary cathode material composition provided by the invention discharges for the first time
It measures as 183.7mAh/g, the near 156.2mAh/g of specific capacity after cycling 300 times, capacity retention ratio is reached for 85%；The present invention provides
Ni-based tertiary cathode material humidity be 80% air in place 30 days after, the ratio of electric discharge for the first time of recomposition lithium ion battery
Capacity is 180.4mAh/g, when not placing compared with, reduced by only after about 3.3mAh/g claddings material after cycle 300 times, than
Capacity decays to 141.6mAh/g, capacity retention ratio 78.5% by 180.4mAh/g.
Description of the drawings
Fig. 1 is the XRD diffraction patterns of Ni-based tertiary cathode material after the cladding prepared in embodiment 1；
Fig. 2 is the TEM figures of Ni-based tertiary cathode material after the uncoated and cladding prepared in embodiment 1；
Fig. 3 is the cycle charge-discharge graph of Ni-based tertiary cathode material after the uncoated and cladding prepared in embodiment 1；
Fig. 4 is C members after Ni-based tertiary cathode material places 30 in air after prepare uncoated and cladding in embodiment 1
The XPS spectrum figure of element；
Fig. 5 is after Ni-based tertiary cathode material places 30 days in air after prepare uncoated and cladding in embodiment 1
For the first time with the 300th charging and discharging curve figure；
Fig. 6 is after Ni-based tertiary cathode material places 30 days in air after prepare uncoated and cladding in embodiment 1
Cycle charge-discharge graph；
Fig. 7 is the cycle charge-discharge graph of Ni-based tertiary cathode material after the cladding prepared in embodiment 2；
Fig. 8 is the cycle charge-discharge graph of Ni-based tertiary cathode material after the cladding prepared in embodiment 3.
Specific embodiment
In order to further appreciate that the present invention, the preferred embodiments of the invention are described with reference to embodiment, but
It is it should be appreciated that these descriptions are simply for the feature and advantage that further illustrate the present invention rather than to patent requirements of the present invention
Limitation.
All raw materials of the present invention, are not particularly limited its source, buying on the market or according to people in the art
Known to member prepared by conventional method.
All raw materials of the present invention, are not particularly limited its purity, pure present invention preferably employs analyzing.
The present invention provides a kind of Ni-based tertiary cathode materials, are compounded in by coupling agent behind nickel-base material surface and carry out heat again
Processing obtains.
The nickel-base material is not particularly limited in the present invention, is used to make lithium ion with well known to those skilled in the art
The Ni-based ternary material of anode or rich nickel cobalt nickel lithium manganate ternary material, chemical formula LiNi1-x-yCoxMnyO2,
The present invention is preferably Ni-based ternary material, and more preferably rich nickel ternary material, the chemical formula of the nickel-base material is preferably such as formula (I)
It is shown,
LiNi1-x-yCoxMnyO2(I)；Wherein, (1-x-y) >=0.5, x ＞ 0, y ＞ 0.
The coupling agent is not particularly limited in the present invention, with coupling agent well known to those skilled in the art, ability
Field technique personnel can make choice according to practical condition, combining case and properties of product, and the present invention is compound to ensure
Effect and positive electrode performance, the coupling agent are preferably the one of titanate coupling agent, aluminate coupling agent and silane coupling agent
Kind is a variety of, more preferably titanate coupling agent, aluminate coupling agent or silane coupling agent；The present invention is coupled the titanate esters
Agent is not particularly limited, and with titanate coupling agent well known to those skilled in the art, the present invention is particularly preferred as titanate esters
DNZ-101 and/or titanate esters DNZ-311；The aluminate coupling agent is not particularly limited in the present invention, with people in the art
Aluminate coupling agent known to member, the present invention are particularly preferred as ester aluminate DL-411, ester aluminate DL-411 AF, Aluminate
One or more of DL-411D and Aluminate ASA；The silane coupling agent is not particularly limited in the present invention, with this field
Silane coupling agent known to technical staff, the present invention are particularly preferred as Silane coupling agent KH550 and/or silane coupling agent
KH560。
The present invention to it is described it is compound be not particularly limited, with composite definitions well known to those skilled in the art, this hair
It is bright be preferably cladding, half cladding, modification, be stacked or generation, more preferably cladding or half coat, most preferably coat or modify.
The cladding is not particularly limited in the present invention, is defined with cladding well known to those skilled in the art, the present invention is preferably
Full cladding.The mass ratio of the coupling agent and the nickel-base material is not particularly limited in the present invention, and those skilled in the art can
To be made choice according to practical condition, cladding situation and properties of product, coupling agent of the present invention and the Ni-based material
The mass ratio of material is preferably (0.005~0.1):1, more preferably (0.01~0.09):1, more preferably (0.02~0.08):1,
Most preferably (0.04~0.06):1.The heat treatment is not particularly limited in the present invention, with well known to those skilled in the art
Heat treatment mode.
The present invention is coated using coupling agent or modified on nickel-base material surface, has obtained Ni-based tertiary cathode material, i.e., one
Kind surface coating modification or surface modified Ni-based tertiary cathode material.The present invention is for existing nickel-base material due to nickel
Content is high, when material exposes in air, the O in material surface lattice2–It can be with the CO in air2Or H2O reaction generations
CO3 2–Or OH–, the Li of material surface remnants is (with Li2The presence of O forms) will and CO3 2–Or OH–Reaction generation Li2CO3Or
LiOH, these material surface formed impurity can seriously affect the processing performance and chemical property of material the problem of.This
Outside, these impurity also aggravate the decomposition of electrolyte, and the HF of generation causes the corrosion to material granule surface, and then affects Xun Huan
The defects of performance.Using the hydroxyl of the surface functional group in coupling agent and positive electrode particle surface chemical bond occurs for the present invention
Conjunction process, mainly including spontaneous hydrolysis, condensation, formation hydrogen bond or covalent bond so that one layer of the particle surface cladding of material is organic
Film, and then effectively reduce the surface corrosion phenomenon during the influence and use of nickel-base material surface impurity；Simultaneously also
Improve the hydrophilic surface nature of Ni-based tertiary cathode material, efficiently solve Ni-based tertiary cathode material to Environmental Water compared with
Sensitive issue reduces the remaining lithium content of particle surface
The present invention provides a kind of preparation methods of Ni-based tertiary cathode material, comprise the following steps, comprise the following steps：
1) by after nickel-base material presoma and lithium salts mixed calcining, nickel-base material is obtained；
Shown in the chemical formula of the nickel-base material such as formula (I),
LiNi1-x-yCoxMnyO2(I)；Wherein, (1-x-y) >=0.5, x ＞ 0, y ＞ 0；
2) above-mentioned steps are obtained nickel-base material and coupling agent to react in organic solvent, then it is fired after, obtain
Ni-based tertiary cathode material.
The present invention especially indicates the optimum principles such as the selection of the raw material and ratio, such as nothing, with foregoing Ni-based ternary just
Consistent in the material of pole, this is no longer going to repeat them.
The present invention by after nickel-base material presoma and lithium salts mixed calcining, obtains nickel-base material first.
The nickel-base material presoma is not particularly limited in the present invention, with Ni-based ternary well known to those skilled in the art
Positive electrode material precursor, the present invention are preferably nickel cobalt manganese hydroxide, more preferably have the chemistry as shown in formula (II)
Formula,
Ni1-x-yCoxMny(OH)2(II)；Wherein, (1-x-y) >=0.5, x ＞ 0, y ＞ 0.
The source of the nickel-base material presoma is not particularly limited in the present invention, and those skilled in the art can be according to normal
Rule method is prepared or commercially；The present invention is to the specific element ratio of the nickel-base material presoma without spy
It does not limit, with the element ratio of Ni-based ternary anode material precursor well known to those skilled in the art, the preferred institute of the present invention
Nickel in nickel-base material presoma is stated, molar ratio of the three kinds of elements of cobalt and manganese respectively in terms of nickel cobalt manganese Metal is preferably 1：(0.1~
1)：(0.1~1), more preferably 1：(0.2~0.8)：(0.2~0.8), more preferably 1：(0.3~0.6)：(0.3~0.6),
Most preferably 1：(0.4~0.5)：(0.4~0.5) can be 1 illustratively:1:1、2:2:1、2:1:2、5:2:3、3:1:1、
7:1.5:1.5、8:1:Any one in 1.
The lithium salts is not particularly limited in the present invention, and Ni-based ternary is being used to prepare just with well known to those skilled in the art
The lithium salts of pole material, the present invention are preferably the one or more in lithium carbonate, lithium hydroxide, lithium nitrate and lithium acetate, more
Preferably lithium carbonate, lithium hydroxide, lithium nitrate or lithium acetate are most preferably lithium hydroxide, lithium nitrate or lithium acetate.Institute of the present invention
It is preferably 1 to state nickel-base material presoma and the molar ratio of the lithium salts：(1.01~1.10), more preferably 1：(1.02~
1.09), it is more preferably 1：(1.03~1.08) are most preferably 1：(1.04~1.07)；The above-mentioned nickel-base material presoma of the present invention
Molal quantity be that molal quantity summation in terms of nickel cobalt manganese Metal calculates, the molal quantity of above-mentioned lithium salts is the molal quantity of lithium metal meter
It calculates.
The nickel-base material is not particularly limited in the present invention, with the Ni-based tertiary cathode of richness well known to those skilled in the art
Material, the present invention are preferably Ni-based tertiary cathode material, shown in the chemical formula such as formula (I) of the more preferable nickel-base material,
LiNi1-x-yCoxMnyO2(I)；Wherein, (1-x-y) >=0.5, x ＞ 0, y ＞ 0.
The condition of the mixing is not particularly limited in the present invention, with the mixed of such reaction well known to those skilled in the art
Conjunction condition, those skilled in the art can be adjusted according to practical condition, raw material condition, and the present invention is preferably equal
Even mixing, the time of the mixing is preferably 3~6h, more preferably 4~5h；The present invention is not special to the mode of the mixing
Limitation, with hybrid mode well known to those skilled in the art, the present invention is preferably to be stirred.
The condition of the calcining is not particularly limited in the present invention, with tertiary cathode material well known to those skilled in the art
Calcination condition, those skilled in the art can be adjusted according to practical condition, product situation and performance requirement
Whole, the temperature of calcining of the present invention is preferably 700~1000 DEG C, more preferably 750~950 DEG C, is most preferably 800~900
℃；The time of the calcining is preferably 4~20h, more preferably 6~18h, more preferably 8~16h, is most preferably 10~14h；
The other conditions of the calcining are not particularly limited in the present invention, with calcination condition well known to those skilled in the art.
Above-mentioned steps are then obtained nickel-base material and coupling agent and reacted in organic solvent by the present invention, then fired
Afterwards, Ni-based tertiary cathode material is obtained.
The organic solvent is not particularly limited in the present invention, with organic solvent well known to those skilled in the art,
The present invention is preferably the one or more in ethyl alcohol, n-butanol, ethylene glycol, isopropanol and acetone, more preferably ethyl alcohol, positive fourth
Alcohol, ethylene glycol, isopropanol or acetone are most preferably ethyl alcohol, n-butanol, isopropanol or acetone.The present invention is to the organic solvent
Dosage be not particularly limited, it is of the present invention Ni-based with organic solvent conventional amount used well known to those skilled in the art
The mass ratio of material and organic solvent is preferably 1:(1~5), more preferably 1:(1.5~4.5), more preferably 1:(2~4), most
Preferably 1:(2.5~3.5).
The condition of the reaction is not particularly limited in the present invention, and those skilled in the art can be according to actual production feelings
Condition, product situation and performance requirement are adjusted, and the temperature of reaction of the present invention is preferably 50~90 DEG C, and more preferably 65
~85 DEG C, be most preferably 60~80 DEG C；The time of the reaction is preferably 0.5~5h, more preferably 1~4h, most preferably 1~
2h.Reactive mode of the present invention is not particularly limited, and the present invention is preferably to be stirred to react, and the mixing speed is preferably 300
~700 turns/min, more preferably 400~600 turns/min.The present invention does not limit the post processing mode after the reaction especially
System, with conventional post processing mode well known to those skilled in the art, those skilled in the art can be according to actual production feelings
Condition, product situation and performance requirement are adjusted, and the present invention is preferably after reaction, to be filtered step while hot, then
The postprocessing working procedures such as washed and dried；The present invention is to the above-mentioned actual conditions for the postprocessing working procedures such as being filtered, washed and dried
It is not particularly limited, with the condition of above-mentioned postprocessing working procedures well known to those skilled in the art.
The condition of the roasting is not particularly limited in the present invention, with constant temperature calcining condition well known to those skilled in the art
, those skilled in the art can be adjusted according to practical condition, product situation and performance requirement, institute of the present invention
The temperature for stating roasting is preferably 200~600 DEG C, more preferably 250~500 DEG C, is most preferably 300~400 DEG C；The roasting
Time is preferably 1~5h, more preferably 1.5~4.5h, is most preferably 2~4h；The present invention does not have the other conditions of the roasting
There is special limitation, with roasting condition well known to those skilled in the art, the present invention further preferably carries out under protective atmosphere
Roasting；The protective atmosphere is not particularly limited in the present invention, with the common protective atmosphere of those skilled in the art,
The present invention is preferably nitrogen or inert gas.
The present invention carries out recombination reaction in non-aqueous system, simple and convenient, without adjusting pH and not introducing impurity anions
Technological process, during effectively solving existing cladding, generally use metal brine system, precipitation reaction is coated
Object, and the dissolving of nickel-base material surface metal and the missing of lithium are easily caused in precipitation reaction and washing filter process, it leads
Causing the specific capacity of material reduces, and operating procedure is cumbersome, and industrialization difficulty is larger, and mostly containing the useless of remaining anion
The problems such as water process.
The present invention is prepared for Ni-based tertiary cathode material, a kind of Ni-based ternary of coupling agent coating modification by above-mentioned steps
Positive electrode, the present invention use coupling agent as compound material, be substantially coupling agent during cladding, contain in coupling agent molecule
There are two types of groups, and one kind is hydrophilic radical, chemical reaction can occur with inorganic powder surface and cause inorganic powder surface cladding
One layer of organic film, to reduce the surface of inorganic particle energy, changes its hydrophilic surface nature；Another group is hydrophobic group
Group can react or tangle with high molecular polymer, function served as bridge served as between inorganic particle and high molecular polymer so that nothing
Machine powder is firmly bonded in high molecular polymer.So as to improve the surface nature that Ni-based tertiary cathode material is hydrophilic, have
Effect overcomes Ni-based tertiary cathode material since nickel content is high, when material exposes in air, the Li of material surface remnants
Alkaline, lithium salt impurity can be generated, the processing performance of material and cycle performance and the defects of high rate performance can be seriously affected, from
And solve the problems, such as that Ni-based tertiary cathode material is more sensitive to Environmental Water, the remaining lithium content of particle surface is reduced,
Improve later stage processability.
The present invention forms the metal oxide or lithiumation of layer structure stabilization after cryogenic thermostat roasts, in particle surface
Metal oxide composite membrane reduces positive electrode in cyclic process easily by the hydrolysate HF corrosion of electrolyte and so that following
The phenomenon that ring service life reduction.And as a result of non-aqueous system, because of the Ni-based tertiary cathode material electric discharge ratio without caused by
The loss of capacity, and the dissolving of the particle surface transition metal ions in long-term cyclic process can be inhibited, reduce charge and discharge
Corrosion of the HF generated in the process to material surface improves the chemical property of material.
The present invention carries out performance detection, experimental result table to the above-mentioned lithium ion battery being made of Ni-based tertiary cathode material
Bright, the lithium ion battery first discharge specific capacity of Ni-based tertiary cathode material composition provided by the invention is 183.7mAh/g, is followed
The near 156.2mAh/g of specific capacity after ring 300 times, capacity retention ratio are reached for 85%；Ni-based tertiary cathode material provided by the invention
After being placed 30 days in the air for being 80% in humidity, the first discharge specific capacity of recomposition lithium ion battery is 180.4mAh/g,
Compared with when not placing, material is reduced by only after about 3.3mAh/g claddings after cycle 300 times, specific capacity is declined by 180.4mAh/g
It is kept to 141.6mAh/g, capacity retention ratio 78.5%.
For a further understanding of the present invention, with reference to embodiment to a kind of Ni-based tertiary cathode material provided by the invention
And preparation method thereof illustrate, protection scope of the present invention is not limited by the following examples.
Embodiment 1
By commercialized Ni-based Ni0.8Co0.1Mn0.1(OH)2Presoma is with lithium hydroxide according to Li:(Ni+Co+Mn)=
1.03:The 1 molar ratio high-temperature calcination 10h at 800 DEG C after mixing, cooling, crush, sieving obtain it is uncoated Ni-based
Positive electrode is uncoated material.
Uncoated nickel-base anode material obtained above is added in absolute ethyl alcohol, Ni-based tertiary cathode material and nothing
The mass ratio of water-ethanol is 1:2, it is 0.01 according to the mass ratio of Ni-based tertiary cathode material after agitated high speed dispersion:1
Addition adds in titanate coupling agent, and the reaction temperature of control system is 55 DEG C, and mixing speed is 400 turns/min, when reaction 1 is small
It filters while hot afterwards, the constant temperature calcining 2h at 300 DEG C, the Ni-based tertiary cathode that oxide cladding is decomposed by titanate coupling agent is made
Material, material after as coating.
Referring to Fig. 1, Fig. 1 is the XRD diffraction patterns of Ni-based tertiary cathode material after the cladding prepared in embodiment 1；Referring to figure
2, Fig. 2 be the TEM figures of Ni-based tertiary cathode material after the uncoated and cladding prepared in embodiment 1.As shown in Figure 1, after cladding
Composite positive pole substantially and LiNiO2Standard diagram coincide, and illustrates that cladding will not have an impact material structure, Neng Goubao
Hold former LiNiO2Basic structure.As shown in Figure 2, it is about 20- uniformly to have coated a layer thickness on the surface of positive electrode
The metal oxide or lithiated metal oxide composite membrane that a layer structure of 50nm is stablized.
Using the uncoated of above-mentioned preparation and cladding latter two material as active material, using lithium piece as cathode, true
CR2025 button cells are assembled into empty-handed casing, cycle performance test is carried out at 25 DEG C using blue electric battery test system.
Its test voltage scope is 2.8~4.3V, is respectively cycled 300 times in the case where charging and discharging currents is 1C, investigates capacity retention ratio.
Referring to Fig. 3, Fig. 3 is the cycle charge discharge of Ni-based tertiary cathode material after the uncoated and cladding prepared in embodiment 1
Electric graph, as shown in the cycle performance test of Fig. 3, uncoated material 1C first discharge specific capacities are 184.7mAh/g, are cycled
The near 118.6mAh/g of specific capacity after 300 times, capacity retention ratio are only 64.2%；And material 1C first discharge specific capacities after coating
For 183.7mAh/g, the near 156.2mAh/g of specific capacity after cycling 300 times, capacity retention ratio is reached for 85%.It can be seen that in this technique
Under, greatly improve the cycle performance of nickel-base material.
To investigate influence of the present invention to nickel-base material surface texture and shelf characteric, the uncoated material and bag that will be obtained
After being placed 30 days in the air that material after covering is 80% in humidity, using the Li of XPS qualitative analysis material surfaces2CO3Impurity
Content, and material after the uncoated material after placement and cladding is assembled into CR2025 button cells according to the method described above and carries out electricity
Chemical property test comparison.
Referring to Fig. 4, Fig. 4 is that Ni-based tertiary cathode material is put in air after prepare uncoated and cladding in embodiment 1
Put the XPS spectrum figure of C element after 30.As shown in the XPS spectrum figure of Fig. 4 carbons, comparison represents material surface Li2CO3Impurity contains
The combination energy peak intensity of amount can be seen that the peak intensity of material after cladding significantly lower than uncoated material, illustrate even in titanate esters
After joining agent coating modification, the inorganic lithium metal-oxide film of titaniferous is formd in particle surface can significantly avoid air
Moisture and particle surface side reaction occurs, reduce Li2CO3Or the generation of the impurity such as LiOH.
Referring to Fig. 5, Fig. 5 is that Ni-based tertiary cathode material is put in air after prepare uncoated and cladding in embodiment 1
Put after 30 days for the first time with the 300th charging and discharging curve figure.As shown in the charging and discharging curve of Fig. 5, place in air identical
After time, material first discharge specific capacity differs larger, the electric discharge specific volume for the first time of material after cladding after uncoated material and cladding
Measure as 180.4mAh/g, when not placing compared with, reduced by only about 4mAh/g, and the first discharge specific capacity of uncoated material is only
For 160.4mAh/g, it is very big to reduce amplitude.The voltage platform of the charging and discharging curve of the 300th time of uncoated material has disappeared,
And material still keeps certain discharge voltage plateau after coating.This is because uncoated material places 30 days rear surfaces in air
Li2CO3Impurity content is higher so that Charge-transfer resistance greatly increases, and lithium ion transport is obstructed, and the polarization of battery is caused to show
As more serious, and this phenomenon is significantly improved after titanate coupling agent decomposes oxide coating modification, improve material
Shelf characteric.
Referring to Fig. 6, Fig. 6 is that Ni-based tertiary cathode material is put in air after prepare uncoated and cladding in embodiment 1
Put the cycle charge-discharge graph after 30 days.As shown in the test of Fig. 6 cycle performances, after placing the identical time in air, bag
Rear material is covered after cycling 300 times, and specific capacity decays to 141.6mAh/g, capacity retention ratio 78.5% by 180.4mAh/g.
And after uncoated material circulation 300 times, specific capacity decays to 83.2mAh/g, capacity retention ratio 51.8% by 160.4mAh/g.
Embodiment 2
By commercialized Ni-based Ni0.5Co0.2Mn0.3(OH)2Presoma is with lithium carbonate according to Li:(Ni+Co+Mn)=1.04:
The high-temperature calcination 12h at 900 DEG C, cooling, crushing, sieving obtain nickel-base material to 1 molar ratio after mixing.
Nickel-base material obtained above is added in isopropanol, the mass ratio of Ni-based tertiary cathode material and isopropanol is
1:3, it is 0.02 according to the mass ratio of Ni-based tertiary cathode material after agitated high speed dispersion:1 addition adds in Aluminate
Coupling agent, the reaction temperature of control system are 60 DEG C, and mixing speed is 500 turns/min, when reaction 1.5 is small after filter while hot, in
The Ni-based tertiary cathode material that oxide cladding is decomposed by aluminate coupling agent is made in constant temperature calcining 3h at 400 DEG C.
Using Ni-based tertiary cathode material after the cladding of above-mentioned preparation as active material, using lithium piece as cathode, in vacuum hand
CR2025 button cells are assembled into casing, cycle performance test is carried out at 25 DEG C using blue electric battery test system.It is surveyed
Examination voltage range is 2.7~4.2V, is cycled 500 times in the case where charging and discharging currents is 0.5C, investigates capacity retention ratio.
Referring to Fig. 7, Fig. 7 is the cycle charge-discharge graph of Ni-based tertiary cathode material after the cladding prepared in embodiment 2.
As shown in the cycle performance test of Fig. 7, material 0.5C first discharge specific capacities are 151.3mAh/g after cladding, after cycling 500 times
The near 129.5mAh/g of specific capacity, capacity retention ratio 85.6%.
Embodiment 3
By commercialized Ni-based Ni0.6Co0.2Mn0.2(OH)2Presoma is with lithium hydroxide according to Li:(Ni+Co+Mn)=
1.06:The high-temperature calcination 15h at 850 DEG C, cooling, crushing, sieving obtain Ni-based tertiary cathode to 1 molar ratio after mixing
Material.
Ni-based tertiary cathode material obtained above is added in ethylene glycol, Ni-based tertiary cathode material and ethylene glycol
Mass ratio is 1:4, it is 0.03 according to the mass ratio of Ni-based tertiary cathode material after agitated high speed dispersion:1 addition adds
Enter silane coupling agent, the reaction temperature of control system is 70 DEG C, and mixing speed is 600 turns/min, when reaction 2 is small after mistake while hot
The Ni-based tertiary cathode material that oxide cladding is decomposed by silane coupling agent is made in filter, the constant temperature calcining 4h at 500 DEG C.
Using nickel-base material after the cladding of above-mentioned preparation as active material, using lithium piece as cathode, the group in vacuum glove box
CR2025 button cells are dressed up, cycle performance test is carried out at 25 DEG C using blue electric battery test system.Its test voltage model
It encloses for 3.0~4.3V, cycle 500 times in the case where charging and discharging currents is 0.5C, investigation capacity retention ratio.
Referring to Fig. 8, Fig. 8 is the cycle charge-discharge graph of Ni-based tertiary cathode material after the cladding prepared in embodiment 3.
As shown in the cycle performance test of Fig. 8, material 0.5C first discharge specific capacities are 175.3mAh/g after cladding, after cycling 500 times
The near 148.5mAh/g of specific capacity, capacity retention ratio 84.7%..
A kind of Ni-based tertiary cathode material provided by the invention and preparation method thereof is described in detail above, this
Specific case is applied in text to be set forth the principle of the present invention and embodiment, the explanation of above example is only intended to
It helps to understand method and its core concept of the invention, it is noted that for those skilled in the art,
Without departing from the principles of the invention, can also to the present invention some improvement and modification can also be carried out, these improvement and modification also fall
Enter in the protection domain of the claims in the present invention.
Claims (9)
1. a kind of preparation method of Ni-based tertiary cathode material, which is characterized in that comprise the following steps：
1) by after nickel-base material presoma and lithium salts mixed calcining, nickel-base material is obtained；
2) above-mentioned steps are obtained nickel-base material and coupling agent to react in organic solvent, then it is fired after, obtain Ni-based
Tertiary cathode material；
The temperature of the roasting is 300~600 DEG C.
2. preparation method according to claim 1, which is characterized in that the coupling agent is titanate coupling agent, Aluminate
The one or more of coupling agent and silane coupling agent.
3. preparation method according to claim 1, which is characterized in that shown in the chemical formula of the nickel-base material such as formula (I),
LiNi1-x-yCoxMnyO2(I)；Wherein, (1-x-y) >=0.5, x ＞ 0, y ＞ 0；
The mass ratio of the coupling agent and the nickel-base material is (0.005~0.1):1.
4. preparation method according to claim 1, which is characterized in that the nickel-base material presoma is nickel cobalt manganese hydroxide
Object, shown in chemical formula such as formula (II),
Ni1-x-yCoxMny(OH)2(II)；Wherein, (1-x-y) >=0.5, x ＞ 0, y ＞ 0.
5. preparation method according to claim 1, which is characterized in that the lithium salts is lithium carbonate, lithium hydroxide, lithium nitrate
With the one or more in lithium acetate；
The molar ratio of the nickel-base material presoma and the lithium salts is 1：(1.01~1.10).
6. preparation method according to claim 1, which is characterized in that the temperature of the calcining is 700~1000 DEG C, described
The time of calcining is 4~20h.
7. preparation method according to claim 1, which is characterized in that the organic solvent includes ethyl alcohol, n-butanol, second two
One or more in alcohol, isopropanol and acetone；
The mass ratio of the nickel-base material and organic solvent is 1:(1~5).
8. preparation method according to claim 1, which is characterized in that the temperature of the reaction is 50~90 DEG C, described anti-
The time answered is 0.5~5h.
9. preparation method according to claim 1, which is characterized in that the time of the roasting is 1~5h.
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| CN106299299A (en) * | 2016-09-21 | 2017-01-04 | 哈尔滨工业大学 | A kind of anode material for lithium-ion batteries with surface hydrophobic and preparation method thereof |
| CN108155352A (en) * | 2016-12-06 | 2018-06-12 | 天津国安盟固利新材料科技股份有限公司 | A kind of anode material for lithium-ion batteries with water resistance and preparation method thereof |
| CN107785555A (en) * | 2017-10-30 | 2018-03-09 | 华中科技大学 | A kind of lithium ion battery, modification lithium-ion battery anode material and preparation method thereof |
| CN109950530A (en) * | 2017-12-21 | 2019-06-28 | 天津国安盟固利新材料科技股份有限公司 | With the nickelic tertiary cathode material and preparation method thereof for improving electrical property |
| CN109994712B (en) * | 2017-12-29 | 2022-04-08 | 湖北九邦新能源科技有限公司 | Surface-modified high-nickel ternary cathode material, modification method thereof and lithium ion battery |
| CN108376784B (en) * | 2018-03-08 | 2020-12-04 | 西北工业大学 | Method for improving moisture absorption of ternary cathode material and slurry gelation phenomenon |
| CN109817902B (en) * | 2018-12-25 | 2021-09-28 | 江苏理工学院 | Method for improving battery cycle stability by using bimetallic coupling agent |
| CN110364719A (en) * | 2019-07-25 | 2019-10-22 | 苏州大学 | The nickelic metal oxide materials and preparation method thereof of silicon oxygen modification |
| CN110828795B (en) * | 2019-10-29 | 2022-06-03 | 陈璞 | Zinc-manganese-oxygen cathode material and preparation method and application thereof |
| CN111600023B (en) * | 2020-04-09 | 2022-04-19 | 中南大学 | Titanium dioxide coated nickel-cobalt-manganese ternary cathode material and preparation method and application thereof |
| CN111600022B (en) * | 2020-04-09 | 2021-08-24 | 中南大学 | Tin dioxide coated nickel cobalt lithium manganate material and preparation method and application thereof |
| CN111600024B (en) * | 2020-04-09 | 2022-02-11 | 中南大学 | Aluminum oxide coated Ni-Co-Mn ternary lithium battery positive electrode material and preparation method and application thereof |
| CN111785973B (en) * | 2020-08-20 | 2021-09-10 | 中南大学 | Organic matter double-layer coated ternary cathode material and preparation and application thereof |
| CN112117451A (en) * | 2020-09-29 | 2020-12-22 | 山东省科学院能源研究所 | Mixed-phase titanium dioxide modified high-nickel ternary cathode material and preparation method and application thereof |
| CN112820865A (en) * | 2021-02-05 | 2021-05-18 | 合肥国轩高科动力能源有限公司 | Preparation method of double-layer surface-coated high-nickel ternary single crystal positive electrode material |
| WO2024037143A1 (en) * | 2023-06-08 | 2024-02-22 | 广东邦普循环科技有限公司 | Outer-coating-coated high-nickel ternary positive electrode material and preparation method therefor |
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