CN108123128A - Adulterate Al in a kind of surface layer3+NCM tertiary cathode materials preparation method - Google Patents
Adulterate Al in a kind of surface layer3+NCM tertiary cathode materials preparation method Download PDFInfo
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Abstract
The present invention relates to a kind of surface layers to adulterate Al3+NCM tertiary cathode materials preparation method, belong to field of chemical energy storage battery.The method of the invention is to add in aluminum nitrate during nickel cobalt manganese hydroxide precursor is mixed with lithium hydroxide, so as to fulfill Al3+On surface layer, lithium layer is adulterated；With in nickel cobalt manganese hydroxide precursor preparation process by Al3+It is entrained in transition metal layer to compare, Al3+Being present in lithium layer can preferably play a supporting role, and can use less Al3+Doping has the function that rock-steady structure, especially notable to the chemical property improvement under high voltage high magnification.The method of the invention is easy to operate, and technique and technology are easy to implement, can be with large-scale commercial application, and this method can be used for carrying out Al to the surface of other tertiary cathode materials or lithium-rich anode material3+Doping.
Description
Technical field
The present invention relates to a kind of Al is adulterated on the surface layer of NCM tertiary cathode materials3+Method, belong to chemical energy storage battery
Field.
Background technology
At present, the fossil energies increasingly depleted such as coal, oil, natural gas, in addition, problem of environmental pollution is increasingly becoming various countries
The Important Problems of concern.The development that pure electric automobile and oil and gas mix electrical automobile is more and more of interest by people.This just needs lithium two
Primary cell fast development is to meet active demand of the people for new energy battery practical application.In the family of lithium secondary battery,
Cobalt acid lithium, LiFePO4 and ternary material performer key player in the market successively.It is small-sized convenient that cobalt acid lithium is applied to more
Formula electronic equipment, and LiFePO4 just progressively substitutes it in power electric vapour since specific discharge capacity is relatively low by ternary material
The effect played in terms of vehicle.After tesla's issue in 2012 using NCA (Li [Ni0.85Co0.1Al0.05]O2) tertiary cathode material
After the electric vehicle Model S of power battery, study tertiary cathode material all over the world (including NCM and NCA)
Tide constantly raises.China is new to meet also in development high voltage, the nickelic anode ternary material (NCM, NCA) done one's utmost
The requirement of generation high-capacity electrode material.
NCM(Li[NixCoyMn1-x-y]O2, x>0.5) tertiary cathode material have higher specific discharge capacity (>200 mAh/
G), realize and mentioned in China's new-energy automobile emphasis special project, the energy of industrialization lithium ion battery is realized to the year two thousand twenty
Density reaches more than 300Wh/Kg, cost is down to the most potential positive battery materials of 0.8 yuan/below Wh targets.But at present
NCM tertiary cathode materials obtain extensive commercial applications not yet, one of the main reasons for this be exactly its stable circulation performance and
High rate performance is poor.This is because segregation can occur in NCM tertiary cathode material building-up processes for Ni elements and rich on surface
Collection, and Li+And Ni2+Ionic radius it is close, then in charge discharge cyclic process, it is easy to Li occur+/Ni2+It is mixed
Row, the structure of NCM tertiary cathode materials is made to change, so as to influence the electrochemical stability of NCM tertiary cathode materials and
Electrochemistry cycle performance (Nickel-Rich and Lithium-Rich Layered Oxide Cathodes: Progress
And Perspectives, Arumugam Manthiram, James C.Knight, Seung-Taek Myung, Seung-Min
Oh,and Yang-Kook Su,Adv.Energy Mater.2016,6,1501010)。
It is understood by numerous studies, Al is adulterated in NCM tertiary cathode materials3+, due to Al3+Chemical inertness, filling
Electrochemical reaction is not involved in discharge process, phase transformation of the NCM tertiary cathode materials during repeated charge can be inhibited,
So as to improve the chemical property of NCM tertiary cathode materials.It is currently in NCM tertiary cathode material precursor building-up processes
Realize Al3+Doping, i.e. Al3+With Ni2+、Co2+And Mn2+Co-precipitation, then Al3+It will be even into stratiform NCM tertiary cathodes
Transition metal layer (Phases Formed in Al-Doped Ni inside material lattice1/3Mn1/3Co1/3(OH)2Prepared
by Coprecipitation:Formation of Layered Double Hydroxide, Xuemei Zhao, Fu
Zhou,and J.R.Dahn, Journal of Electrochemical Society,155(9)A642-A647(2008))。
Due to Al3+Uniform Doped is in the transition metal layer of NCM tertiary cathode materials, and NCM tertiary cathode material structure collapses are main
Be due in lithium layer a large amount of lithium ions it is embedding go out, be easy to cause caused by lithium layer caves in, so being entrained in transition metal layer Al3+It is right
It is limited in the effect that inhibition lithium layer is caved in, effect especially is improved to the chemical property under high voltage high magnification (4.5V, >=1C)
Fruit is bad.
The content of the invention
The doping Al prepared for the prior art3+Electrochemistry of the NCM tertiary cathode materials under high voltage high magnification
Can be bad the problem of, it is an object of the invention to provide a kind of surface doping Al3+NCM tertiary cathode materials preparation method,
This method is to carry out Al during the presoma of NCM tertiary cathode materials is mixed with lithium salts3+Doping, so as to real
Existing Al3+The doping of lithium layer in NCM tertiary cathode materials surface layer, a large amount of lithium ions it is embedding go out when, Al3+It can be effective in lithium layer
Maintain lattice structure stabilization, retain more reversible lithium positions, ensure that lithium ion insertion/it is embedding go out invertibity, so as to improve
The chemical property of NCM tertiary cathode materials, especially to the chemical property under high voltage high magnification (4.5V, >=1C)
There is significant improvement.
The purpose of the present invention is what is be achieved through the following technical solutions.
Adulterate Al in a kind of surface layer3+NCM tertiary cathode materials preparation method, Al is adulterated on the surface layer3+NCM ternarys
The chemical formula of positive electrode is Li1-xAlx[Ni0.8Co0.1Mn0.1]O2, wherein 0.005≤x≤0.02；
The method step is as follows,
By nickel cobalt manganese hydroxide precursor powder (Ni0.8Co0.1Mn0.1(OH)2), aluminum nitrate powder and lithium hydroxide
Powder after mixing, then is placed under oxygen atmosphere and is calcined；Wherein, 4h~6h is first kept the temperature at 450 DEG C~550 DEG C, then
It is warming up to 750 DEG C~850 DEG C and keeps the temperature 12h~20h, furnace cooling obtains surface layer doping Al3+NCM tertiary cathode materials,
It is abbreviated as Al-NCM811.
Wherein, the mole ratio of the molal quantity of lithium hydroxide and nickel cobalt manganese hydroxide precursor powder is (0.98-
0.98x)~(1.05-1.05x):1；The molal quantity of aluminum nitrate and the mole ratio of lithium hydroxide are 1:(49~199).
Further, first lithium hydroxide is added in mortar, dry grind 10min~15min, by lithium hydroxide particulate abrasive
Into powder, then with aluminum nitrate powder ultrasound 2h~5h, then the mixture of lithium hydroxide and aluminum nitrate is transferred to and is ground in ethanol
In alms bowl, and add in nickel cobalt manganese hydroxide precursor powder, dry grind 20min~30min after, add ethyl alcohol wet-milling 20min~
30min, then be placed under oxygen atmosphere and calcined.
Advantageous effect：
(1) the method for the invention is to carry out mixed process addition in nickel cobalt manganese hydroxide precursor powder and lithium salts
Silicon source realizes Al3+On surface layer, lithium layer is adulterated, this is because Al3+Ionic radiusLess than Li+Ion half
FootpathSo Al3+Doping is relatively easy into lithium layer；Compared to Al3+It is present in transition metal layer, Al3+In the presence of
It can preferably play a supporting role in lithium layer, and less Al can be used3+Doping has the function that rock-steady structure,
This is because in high-voltage charging state, a large amount of Li+It is embedding go out, Al3+The stabilization of lattice structure can be effectively maintained in lithium layer, inhibits stratiform knot
Transformation of the structure to spinel structure, while Li can also be inhibited+/Ni2+Mixing retains more reversible lithium positions, can so as to improve
Inverse put capacitance.
(2) since the combination power between Al (s)-O (p) keys is far longer than other M-O (M=Ni, Co or Mn), effectively press down
Made NCM tertiary cathode materials oxygen release under high blanking voltage is serious, lattice structure is unstable, easy recurring structure caves in and
The situation of phase transformation, so doping Al3+Structural stabilities and thermal stability of the NCM811 in electrochemistry cyclic process it is more preferable,
Especially Al3+It is notable to the chemical property improvement under high voltage high magnification to be entrained in surface layer lithium layer.
(3) the method for the invention is easy to operate, and technique and technology are easy to implement, can with large-scale commercial application, and
And this method can be used for carrying out Al to the surface of other tertiary cathode materials or lithium-rich anode material3+Doping.
Description of the drawings
X-ray diffraction (XRD) spectrogram for the NCM811 that Fig. 1 is Al-NCM811 prepared by embodiment 1 and prepared by comparative example 1
Comparison diagram.
Fig. 2 is the CR2025 button cells Xun Huan 1 assembled using Al-NCM811 prepared by embodiment 1 as positive electrode
AC impedance (EIS) test charts all and that cycle is after 10 weeks.
Fig. 3 is the CR2025 button cells Xun Huan 1 assembled using Al-NCM811 prepared by embodiment 1 as positive electrode
Cyclic voltammetric (CV) graphs all and that cycle is after 10 weeks.
Fig. 4 is to be cycled using Al-NCM811 prepared by embodiment 1 as the CR2025 button cells that positive electrode assembles
Before, cycle 1 week and cycle 10 weeks after X-ray diffractogram.
Fig. 5 is to be cycled 1 week as the CR2025 button cells that positive electrode assembles using NCM811 prepared by comparative example 1
With cycle 10 weeks after ac impedance measurement figure.
Fig. 6 is to be cycled 1 week as the CR2025 button cells that positive electrode assembles using NCM811 prepared by comparative example 1
With cycle 10 weeks after cyclic voltammetry curve figure.
The CR2025 button cells that Fig. 7 is the NCM811 prepared using comparative example 1 as positive electrode and assembles cycle before,
X-ray diffractogram after cycling 1 week and cycling 10 weeks.
Fig. 8 is the CR2025 button cells that embodiment 1 assembles and the CR2025 button cells that comparative example 1 assembles in 2.75V
Cycle performance graph under~4.35V voltage ranges and 1C (1C=200mAh/g) multiplying power.
Fig. 9 is the CR2025 button cells that embodiment 1 assembles and the CR2025 button cells that comparative example 1 assembles in 2.75V
Cycle performance graph under~4.5V voltage ranges and 1C (1C=200mAh/g) multiplying power.
Figure 10 is that the CR2025 button cells that embodiment 1 assembles and the CR2025 button cells that comparative example 1 assembles exist successively
In 2.75V~4.5V voltage ranges with cycled respectively under the multiplying power of 0.1C, 0.2C, 1C, 2C, 5C, 10C obtain within 5 weeks it is forthright again
It can figure.
Specific embodiment
To be best understood from the present invention, the present invention is described in further detail with reference to specific embodiment.It should be understood that
, the specific embodiments described herein are merely to illustrate and explain the present invention, are not intended to limit the invention.In addition,
The endpoint of disclosed scope and any value are not limited to the accurate scope or value herein, these scopes or value should
It is interpreted as comprising the value close to these scopes or value.For numberical range, between the endpoint value of each scope, Ge Gefan
It between the endpoint value and individual point value that enclose and can be individually combined with each other between point value and obtain one or more newly
Numberical range, these numberical ranges should be considered as specific open herein.
In following embodiment：
X-ray diffractometer：Instrument model is Rigaku Ultima IV, Japanese；
Ac impedance measurement：CHI604c electrochemical workstations, China；Test voltage is 4.5V, and frequency range is
0.01Hz~0.1MHz, the amplitude of sine wave AC voltage disturbing signal are 5m, using to electrode as reference electrode；
Cyclic voltammetry：CHI660e electrochemical workstations, China；Test voltage section is 2V~4.8V, and scanning is fast
Rate 0.1mV/s；
The assembling and test of CR2025 button cells：By positive electrode (Al-NCM811 or right prepared by Examples 1 to 6
NCM811 prepared by ratio 1), acetylene black, PVDF (Kynoar) is according to 8:1:1 mass ratio is made slurry and is coated in
On aluminium foil, the aluminium foil of the load slurry of drying is cut into the sequin that diameter is about 1cm with slitter and is used as anode, with metal
Lithium piece as cathode, Celgard2300 be membrane, 1M carbonate solution be electrolyte (wherein, solvent be volume ratio be 1:1
Ethylene carbonate and dimethyl carbonate mixed solution, solute LiPF6), CR2025 knobs are assembled into argon gas glove box
Detain battery；Using CT2001AAlnd cell testers to the CR2025 button cells assembled under different current densities
Carry out constant current charge-discharge test, it is 200mA/g to define 1C current densities, charging/discharging voltage section for 2.75 V~4.35V and
2.75V~4.5V, test temperature are 30 DEG C；When high rate performance is tested, respectively in 0.1C, 0.2C, 1C, 2C, 5C, 10C, 0.1C
It is respectively cycled under different current densities 5 weeks, carries out constant current charge-discharge test, wherein, in 2C, 5C, 10C high magnification constant-current charge
Afterwards, when then constant-voltage charge 1 is small or constant-voltage charge is less than 0.05C to current density.
Ni used in Examples 1 to 60.8Co0.1Mn0.1(OH)2It is to be prepared according to the method described in comparative example 1
It obtains.
Embodiment 1
First by LiOHH2O add in mortar in, dry grind 15min after, then with Al (NO3)3·9H2O ultrasound 4h in ethanol,
It then transfers in mortar, and adds in Ni0.8Co0.1Mn0.1(OH)2Powder dry grinds after 25min, adds ethyl alcohol and continue
25min is ground, then the mixture of three is placed in oxygen atmosphere, be first heated to 450 DEG C and keeps the temperature 6h, then is warming up to 750 DEG C
And 12h is kept the temperature, furnace cooling obtains doping Al3+NCM tertiary cathode materials Li0.99Al0.01[Ni08Co0.1Mn0.1]O2, brief note
For Al-NCM811；Wherein, LiOHH2O and Al (NO3)3·9H2The molar ratio of O is 99:1, LiOHH2O with
Ni0.8Co0.1Mn0.1(OH)2Molar ratio be 1.040:1.
CR2025 button cells are assembled into using the Al-NCM811 prepared by embodiment 1 as positive electrode, and carry out phase
The electrochemical property test answered.
It was found from the XRD spectra in Fig. 1, the Al-NCM811 prepared by the present embodiment is not changing original nickelic ternary just
The main crystal structure of pole material NCM811, both typical α-NaFeO2Structure belongs to R-3m space groups.It is most lower in Fig. 1
The vertical line of side is PDF#09-0063, represents perfect layer structure LiNiO2Characteristic peak positions, illustrate lithium layer adulterate Al3+It is front and rear
Nickelic ternary material NCM811 be all perfect layer structure.Al is adulterated by the lithium layer listed in table 13+Front and rear structure cell ginseng
Several variations is understood, by Al3+(003) peak and the ratio at (104) peak after doping significantly increase, it was demonstrated that lithium layer adulterates Al3+
Help to inhibit Li+/Ni2+Mixing, and the ratio increase of c/a, illustrate doping Al3+Shortcut performance afterwards is more preferable.But
It is understood from the partial enlargement XRD diagram at θ=18.5 °~19.5 ° and θ=44 °~45 ° two, (003) peak of Al-NCM811
(104) peak is micro- to low angle offset relative to NCM811, illustrates Al3+Support function is played after into lithium layer and maintains to tie
Structure is stablized, this is beneficial to Li+Insertion and abjection.Further, since the combination power between Al (s)-O (p) keys is far longer than it
Combination power between his M-O (M=Ni, Co or Mn) key is more conducive to inhibit positive electrode oxygen release and phase in a high voltage state
The problem of change, so as to help to improve the electrochemistry cycle performance of NCM811.
To being existed using the Al-NCM811 prepared by the present embodiment as the CR2025 button cells that positive electrode assembles
EIS tests are carried out respectively after being cycled 1 week and 10 weeks under 2.75V~4.5V voltage ranges and 0.1C multiplying powers, and test result is detailed
See Fig. 2；To using the NCM811 prepared by comparative example 1 as the CR2025 button cells that positive electrode assembles 2.75V~
EIS tests are carried out respectively after being cycled 1 week and 10 weeks under 4.5V voltage ranges and 0.1C multiplying powers, and test result refers to Fig. 5.
The charge transfer resistance R of the arc representation positive electrode of low frequency range in Fig. 2 and Fig. 5ct, it can be seen that by first week and follow for 10 weeks
After ring, the charge transfer resistance R of Al-NCM811ctIt is significantly less than the R of NCM811ct, show that Al is adulterated on surface layer3+Positive electrode
In electrochemistry cyclic process, surface layer lattice structure is more stable, the polarization smaller of formation.
To being existed using the Al-NCM811 prepared by the present embodiment as the CR2025 button cells that positive electrode assembles
CV tests are carried out respectively after being cycled 1 week and 10 weeks under 2.75V~4.5V voltage ranges and 0.1C multiplying powers, and test result is detailed
See Fig. 3；To using the NCM811 prepared by comparative example 1 as the CR2025 button cells that positive electrode assembles 2.75V~
CV tests are carried out respectively after being cycled 1 week and 10 weeks under 4.5V voltage ranges and 0.1C multiplying powers, and test result refers to Fig. 6.Root
It is understood according to the test result of Fig. 3 and Fig. 6, the position at peak is almost after first week and 10 weeks are cycled, in the CV of two kinds of positive electrodes
All do not deviate, but the peak intensity after NCM811 is cycled 10 weeks is substantially reduced than the peak intensity after Xun Huan head weeks, and Al-
Peak intensity after NCM811 is cycled 10 weeks is almost unchanged, illustrates that the capacity retention ratio of Xun Huan NCM811 after 10 weeks is lower, that is,
Carrying out the substance of redox contribution capacity reduces.In addition, Al-NCM811 was charging after 10 weeks electrochemistry cycles
Corresponding oxidation peak (Ni at 3.7V in journey2+→Ni3+), it slightly deviates, says to low potential compared to the oxidation peak after Xun Huan first week
Bright the lattice structure of Al-NCM811 is stablized in cyclic process, small, the Li of Surface Polarization reduction+/Ni2+Mixing is reduced, so this
The insertions of Shi Jinhang lithium ions it is embedding go out the required overpotential of process it is lower.
Respectively to Al-NCM811 after being cycled 1 week and 10 weeks under 2.75V~4.5V voltage ranges and 0.1C multiplying powers
XRD tests are carried out, the results are shown in Figure 4；Respectively to cycled under 2.75V~4.5V voltage ranges and 0.1C multiplying powers 1 week with
And NCM811 carries out XRD tests after 10 weeks, as a result as shown in Fig. 7, the vertical line below wherein Fig. 4 and Fig. 7 is PDF#09-0063.
According to the test result of Fig. 4 and Fig. 7, the layer structure of positive electrode is still kept fine after cycling, but basis
Partial enlarged view at 18.5 °~19.5 ° understands, the position at (003) peak has offset, and the peak position of NCM811 is to the angle of elevation
The offset of degree is more serious, illustrates that NCM811 is more notable as the carry out structural lattice of electrochemistry cyclic process reduces, that is,
Say NCM811 in embedding de- Li+During since lattice has occurred in structural instability the structure changes such as collapse so that cell parameter
C values reduce, and Al-NCM811 lattice variations in cyclic process are not notable, have also turned out the Al of doping3+In embedding de- Li+'s
The variation of positive electrode lattice structure is inhibited in the process, is significantly improved structural stability, that is, is improved positive electrode
Cycle performance.
Using the CR2025 button cells assembled using the Al-NCM811 prepared by the present embodiment as positive electrode and
The CR2025 button cells assembled using the NCM811 prepared by comparative example 1 as positive electrode, in 2.75V~4.35V voltages
Section, 1C multiplying powers and 30 DEG C of progress constant current charge-discharge tests, test result refer to Fig. 8；In 2.75V~4.5V voltage zones
Between, 1C multiplying powers and 30 DEG C of progress constant current charge-discharge tests, test result refer to Fig. 9.According to the test result of Fig. 8,
In 2.75V~4.35V voltage ranges, the first all discharge capacity of NCM811 cycles is 170.8mAh/g, cycle putting after 500 weeks
Capacitance be 111.9 mAh/g, capacity retention ratio 65.5%；The first all discharge capacities of Al-NCM811 Xun Huans are 171.3mAh/g,
After cycling 500 weeks discharge capacity be 120.5mAh/g, capacity retention ratio 70.3%, at this point, the cycle performance of Al-NCM811
Cycle performance than NCM811 is slightly good.According to the test result of Fig. 9, in the V voltage ranges of 2.75V~4.5, NCM811
First week discharge capacity is 194mAh/g, and discharge capacity of the cycle after 500 weeks is 44.2mAh/g, capacity retention ratio 22.8%；
The all discharge capacities of head of Al-NCM811 are 192mAh/g, and discharge capacity of the Xun Huan after 500 weeks is 139.8mAh/g, and capacity is kept
Rate is 72.8%, then under high blanking voltage state, Al-NCM811 has a clear superiority in terms of the stability of material is maintained.
Using the CR2025 button cells assembled using the Al-NCM811 prepared by the present embodiment as positive electrode and
The CR2025 button cells assembled using the NCM811 prepared by comparative example 1 as positive electrode, in 2.75V~4.5V voltages
At section and 30 DEG C, cycled respectively under 0.1C, 0.2C, 1C, 2C, 5C and 10C multiplying power 5 weeks successively, test result refers to
Figure 10.According to the test result of Figure 10, Al-NCM811 under high rate capability discharge capacity higher, 10C multiplying powers,
Al-NCM811 discharge capacities are 151.1mAh/g, and NCM811 discharge capacities are 140.6mAh/g, further illustrate Al-
The structure of NCM811 is more stable, and chemical property is more excellent.
Table 1
Embodiment 2
First by LiOHH2O add in mortar in, dry grind 15min after, then with Al (NO3)3·9H2O ultrasound 4h in ethanol,
It then transfers in mortar, and adds in Ni0.8Co0.1Mn0.1(OH)2Powder dry grinds after 25min, adds ethyl alcohol and continue
25min is ground, then the mixture of three is placed in oxygen atmosphere, be first heated to 450 DEG C and keeps the temperature 6h, then is warming up to 750 DEG C
And 12h is kept the temperature, furnace cooling obtains doping Al3+NCM tertiary cathode materials Li0.995Al0.005[Ni08Co0.1Mn0.1]O2, letter
It is denoted as Al-NCM811；Wherein, LiOHH2O and Al (NO3)3·9H2The molar ratio of O is 199:1, LiOHH2O with
Ni0.8Co0.1Mn0.1(OH)2Molar ratio be 1.045:1.
Al-NCM811 prepared by embodiment 2 is assembled into CR2025 button cells as positive electrode and carries out electrochemistry
Performance test.Constant current charge-discharge test, first Zhou Fang electricity are carried out under 2.75V~4.35V voltage ranges, 30 DEG C and 1C multiplying powers
Capacity is 169.8mAh/g, and discharge capacity of the cycle after 500 weeks is 114.5 mAh/g, capacity retention ratio 67.4%.
Constant current charge-discharge test is carried out under 2.75V~4.5V voltage ranges, 30 DEG C and 1C multiplying powers, first week discharge capacity is
189.5mAh/g, discharge capacity of the cycle after 500 weeks is 129.6mAh/g, capacity retention ratio 68.4%.
Embodiment 3
First by LiOHH2O add in mortar in, dry grind 15min after, then with Al (NO3)3·9H2O powders surpass in ethanol
Sound 4h, then transfers in mortar, and adds in Ni0.8Co0.1Mn0.1(OH)2Powder dry grinds after 25min, adds ethyl alcohol simultaneously
Continue to grind 25min, then the mixture of three is placed in oxygen atmosphere, be first heated to 450 DEG C and keeps the temperature 6h, then be warming up to
750 DEG C and 12h is kept the temperature, furnace cooling obtains doping Al3+NCM tertiary cathode materials Li0.985Al0.015[Ni08Co0.1Mn0.1]
O2, it is abbreviated as Al-NCM811；Wherein, LiOHH2O and Al (NO3)3·9H2The molar ratio of O is 65.7:1, LiOHH2O with
Ni0.8Co0.1Mn0.1(OH)2Molar ratio be 1.034:1.
Al-NCM811 prepared by embodiment 3 is assembled into CR2025 button cells as positive electrode and carries out electrochemistry
Performance test.Constant current charge-discharge test, first Zhou Fang electricity are carried out under 2.75V~4.35V voltage ranges, 30 DEG C and 1C multiplying powers
Capacity is 170.1mAh/g, and discharge capacity of the cycle after 500 weeks is 119.4 mAh/g, capacity retention ratio 70.2%.
Constant current charge-discharge test is carried out under 2.75V~4.5V voltage ranges, 30 DEG C and 1C multiplying powers, first week discharge capacity is
190.7mAh/g, discharge capacity of the cycle after 500 weeks is 132.8mAh/g, capacity retention ratio 69.6%.
Embodiment 4
First by LiOHH2O add in mortar in, dry grind 15min after, then with Al (NO3)3·9H2O ultrasound 4h in ethanol,
It then transfers in mortar, and adds in Ni0.8Co0.1Mn0.1(OH)2Powder dry grinds after 25min, adds ethyl alcohol and continue
25min is ground, then the mixture of three is placed in oxygen atmosphere, be first heated to 450 DEG C and keeps the temperature 6h, then is warming up to 750 DEG C
And 12h is kept the temperature, furnace cooling obtains doping Al3+NCM tertiary cathode materials Li0.98Al0.02[Ni08Co0.1Mn0.1]O2, brief note
For Al-NCM811；Wherein, LiOHH2O and Al (NO3)3·9H2The molar ratio of O is 49:1, LiOHH2O with
Ni0.8Co0.1Mn0.1(OH)2Molar ratio be 1.029:1.
Al-NCM811 prepared by embodiment 4 is assembled into CR2025 button cells as positive electrode and carries out electrochemistry
Performance test.Constant current charge-discharge test, first Zhou Fang electricity are carried out under 2.75V~4.35V voltage ranges, 30 DEG C and 1C multiplying powers
Capacity is 168.2mAh/g, and discharge capacity of the cycle after 500 weeks is 113.9 mAh/g, capacity retention ratio 67.7%.
Constant current charge-discharge test is carried out under 2.75V~4.5V voltage ranges, 30 DEG C and 1C multiplying powers, first week discharge capacity is
189.3mAh/g, discharge capacity of the cycle after 500 weeks is 126.4mAh/g, capacity retention ratio 66.8%.
Embodiment 5
First by LiOHH2O add in mortar in, dry grind 10min after, then with Al (NO3)3·9H2O ultrasound 5h in ethanol,
It then transfers in mortar, and adds in Ni0.8Co0.1Mn0.1(OH)2Powder dry grinds after 20min, adds ethyl alcohol and continue
20min is ground, then the mixture of three is placed in oxygen atmosphere, be first heated to 500 DEG C and keeps the temperature 5h, then is warming up to 800 DEG C
And 15h is kept the temperature, furnace cooling obtains doping Al3+NCM tertiary cathode materials Li0.99Al0.01[Ni08Co0.1Mn0.1]O2, brief note
For Al-NCM811；Wherein, LiOHH2O and Al (NO3)3·9H2The molar ratio of O is 99:1, LiOHH2O with
Ni0.8Co0.1Mn0.1(OH)2Molar ratio be 1.01:1.
Al-NCM811 prepared by embodiment 5 is assembled into CR2025 button cells as positive electrode and carries out electrochemistry
Performance test.Constant current charge-discharge test, first Zhou Fang electricity are carried out under 2.75V~4.35V voltage ranges, 30 DEG C and 1C multiplying powers
Capacity is 170.5mAh/g, and discharge capacity of the cycle after 500 weeks is 119.2 mAh/g, capacity retention ratio 69.9%.
Constant current charge-discharge test is carried out under 2.75V~4.5V voltage ranges, 30 DEG C and 1C multiplying powers, first week discharge capacity is
191.4mAh/g, discharge capacity of the cycle after 500 weeks is 128.8mAh/g, capacity retention ratio 67.3%.
Embodiment 6
First by LiOHH2O add in mortar in, dry grind 10min after, then with Al (NO3)3·9H2O ultrasound 2h in ethanol,
It then transfers in mortar, and adds in Ni0.8Co0.1Mn0.1(OH)2Powder dry grinds after 30min, adds ethyl alcohol and continue
30min is ground, then the mixture of three is placed in oxygen atmosphere, be first heated to 550 DEG C and keeps the temperature 4h, then is warming up to 850 DEG C
And 18h is kept the temperature, furnace cooling obtains doping Al3+NCM tertiary cathode materials Li0.99Al0.01[Ni08Co0.1Mn0.1]O2, brief note
For Al-NCM811；Wherein, LiOHH2O and Al (NO3)3·9H2The molar ratio of O is 99:1, LiOHH2O with
Ni0.8Co0.1Mn0.1(OH)2Molar ratio be 0.97:1.
Al-NCM811 prepared by embodiment 6 is assembled into CR2025 button cells as positive electrode and carries out electrochemistry
Performance test.Constant current charge-discharge test, first Zhou Fang electricity are carried out under 2.75V~4.35V voltage ranges, 30 DEG C and 1C multiplying powers
Capacity is 169.4mAh/g, and discharge capacity of the cycle after 500 weeks is 113.8 mAh/g, capacity retention ratio 67.2%.
Constant current charge-discharge test is carried out under 2.75V~4.5V voltage ranges, 30 DEG C and 1C multiplying powers, first week discharge capacity is
187.4mAh/g, discharge capacity of the cycle after 500 weeks is 121.6mAh/g, capacity retention ratio 64.9%.
Comparative example 1
The preparation process of original tertiary cathode material NCM811 undoped with Al is as follows：
(1) according to Mn:Ni:Co=8:1:Manganese sulfate, nickel sulfate and cobaltous sulfate are dissolved in deionized water by 1 molar ratio,
Obtain the sulfate solution of 2mol/L；
(2) alkaline aqueous solution containing 2mol/L sodium carbonate and 2mol/L ammonium hydroxide is configured；
(3) prepared sulfate solution and alkaline aqueous solution are added continuously to peristaltic pump with stirring respectively
In the reaction kettle of device and logical nitrogen, and the addition speed control pH value by adjusting sulfate solution or alkaline aqueous solution, make
PH stabilizes to 11, and controlling reaction temperature is 55 DEG C, and mixing speed 650r/min, sample introduction speed is adjusted to 0.25mL/min；Into
After sample is complete, after keeping ageing 6h in a nitrogen atmosphere, obtained sediment is filtered, wash, is dried, is obtained
Ni0.8Co0.1Mn0.1(OH)2；
(4) by Ni0.8Co0.1Mn0.1(OH)2With LiOH powders according to 1:1.05 molar ratio is mixed, present mortar
Middle dry grinding 25min adds ethyl alcohol and continues to grind 25min, then the mixture of the two is placed in oxygen atmosphere, first heats
To 450 DEG C and 6h is kept the temperature, then is warming up to 750 DEG C and keeps the temperature 12h, furnace cooling obtains NCM tertiary cathode materials, is abbreviated as
NCM811。
CR2025 button cells are assembled into using the NCM811 prepared by comparative example 1 as positive electrode, and are carried out corresponding
Electrochemical property test, test result analysis detailed in Example 1.
It is provided by the invention in NCM tertiary cathode materials by above-described embodiment and the test result of comparative example
Lithium layer doping Al3+Method, the high rate performance of NCM tertiary cathode materials and first all coulombic efficiency can be significantly improved, especially
It is it is more preferably notable to the chemical property improvement under high voltage high magnification, and low cost of raw materials, without poison ring
It protects, entire technological process is simple, efficient, environmental protection, and experiment condition is wide in range, reliability is high, has good prospects for commercial application.
Claims (2)
1. Al is adulterated on a kind of surface layer3+NCM tertiary cathode materials preparation method, it is characterised in that：Adulterate Al in the surface layer3+'s
The chemical formula of NCM tertiary cathode materials is Li1-xAlx[Ni0.8Co0.1Mn0.1]O2, wherein 0.005≤x≤0.02；
The method step is as follows,
By nickel cobalt manganese hydroxide precursor powder, aluminum nitrate powder and lithium hydroxide powder after mixing, then it is placed in oxygen
Calcined under gas atmosphere, first at 450 DEG C~550 DEG C keep the temperature 4h~6h, then be warming up to 750 DEG C~850 DEG C and keep the temperature 12h~
20h, furnace cooling obtain surface layer doping Al3+NCM tertiary cathode materials；
Wherein, the mole ratio of the molal quantity of lithium hydroxide and nickel cobalt manganese hydroxide precursor powder for (0.98-0.98x)~
(1.05-1.05x):1；The molal quantity of aluminum nitrate and the mole ratio of lithium hydroxide are 1:(49~199).
2. a kind of surface layer doping Al according to claim 13+NCM tertiary cathode materials preparation method, feature exists
In：First lithium hydroxide is added in mortar, dry grind 10min~15min, then with aluminum nitrate powder ultrasound 2h~5h in ethanol,
The mixture of lithium hydroxide and aluminum nitrate is transferred in mortar again, and adds in nickel cobalt manganese hydroxide precursor powder, is dry grinded
After 20min~30min, ethyl alcohol wet-milling 20min~30min is added, then is placed under oxygen atmosphere and is calcined.
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| CN110518206A (en) * | 2019-08-22 | 2019-11-29 | 湖北锂诺新能源科技有限公司 | Manganese phosphate vanadium lithium and carbon coat the preparation method of nickel cobalt manganese aluminium composite positive pole altogether |
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| CN114597368A (en) * | 2022-03-15 | 2022-06-07 | 北京理工大学 | Surface sulfur-doped lithium-rich manganese-based layered material with lithium sulfate protective layer |
| CN114597368B (en) * | 2022-03-15 | 2023-10-31 | 北京理工大学 | Lithium-rich manganese-based layered material with surface sulfur doped and lithium sulfate protective layer |
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