Li1.25Mn0,54Ni0,13Co0,13O2 synthesized by spray-drying method using nitrate and acetate precursors
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Transcript of Li1.25Mn0,54Ni0,13Co0,13O2 synthesized by spray-drying method using nitrate and acetate precursors
Li1.25Mn0,54Ni0,13Co0,13O2 synthesized by spray-drying
method using nitrate and acetate precursors Y.M.Koshtyal1, A.M.Rumyantsev1, M.Y.Maximov2, A.O.Silin2, V.V.Zhdanov1
1 Ioffe Institute, 26 Politekhnicheskaya, St Petersburg, 194021, Russia 2 Peter The Great Saint-Petersburg Polytechnic University. 29 Politekhnicheskaya, St Petersburg,
195251, Russia
E-mail [email protected]
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XIV International Conference "Topical Problems of Energy Conversion in Lithium Electrochemical Systems" Suzdal, September 11 – 15, 2016
Changes in production volumes of lithium ion cells employed in Mobile-IT, xEv, ESS applications
2
0
10000
20000
30000
40000
50000
60000
2010 2011 2012 2013 2014 2015
ESS/UPS
xEv
Mobile-IT
MWh/year
Energy density is critical requirement for xEv and Mobile-IT
Source: LIB材料市場速報(15Q1) B3 Corporation. 2015. ‒ 30 p.
Increment of energy density of modern lithium-ion cells by cathode material
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Li ion cell
application
Main
Cathode
Material
Electrode Properties
of cathode
material
How to achieve Means
Mobile IT LiCoO2 Density↑
Tap Density
(PSD)
Particle engineering Calcination, Milling
Sieving ,Mixing
Potential ↑+
Capacity ↑
Stabilized
structure
Doping Metals
Artificial SEI Protective and ion-
conductive coatings
xEv NMC
(NCA)
Density↑
PSD
Density of
particles
Particle engineering
pH, Carbonate / hydroxide;
Rotational speed, Time etc.
+means for LiCoO2
Capacity↑ Ni-
Content↑
Chemistry
ratio of transmission metal
(TM) salts
Stabilized
structure
Doping Metals, Fluorine
Functional coatings Al2O3, AlF3 etc.
Core-shell
Sequence of TM salts
solution injection
*ES 190 Johnson 2014
*ES 049 Thackeray 2013
Lithium-rich cathode materials with “layered-layered” structure
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МО6
Octaedron
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Concept of the research project conducted in partnership with Saint-Petersburg Polytechnic University
Cathode electrodes containing
Lithium-rich “Layered-Layered”
Layers of Al2O3 and SnO2 thin layers obtained by atomic layer deposition
Results of investigations of synthesized lithium-rich materials – presentation Summary of literature review of papers related to modifying of cathode materials by functional thin films obtained by atomic layer deposition – poster session.
Water solution, with concentrations C6H8O7 0.18 М Ni(NO3)2x6H2O 0.06 М Co(NO3)2x6H2O 0.06 М Mn(NO3)2x4H2O 0.25 М LiNO3*3H2O 0.56 М NH4OH 0.90 М pH= ≈6-7 Volume 180 ml
Filtration
Spray drying Büchi B-290 Tin=220°С Tout=130°С Gair=470 l/h Lsol.=3 ml/min Light magenta powder mass ≈ 15 g
Pressing into tablets Mass of a tab 0.5÷1.0 g
Preliminary calcination Т=400-500°С Black powder ≈4-5 fold mass decrease
Calcination Heating time – 2 h The holding time at the temperature – 5-10 h Т=800-900°С Mass decrease 20%
Synthesis of cathode materials by spray-drying method
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Precursors Tcalc.,
°C
Time,
h
SEM PSD XRD EI
Nitrate 800 5 X X X
800 10 X X
900 8 X X X X
Acetate 900 8 X
800 6 X X X
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Microstructure of cathode materials obtained from acetate precursors
Secondary Primary
According to EDX analysis the transition metal ratio is Ni/Co/Mn = 0.13/0.14/0.57
Microstructure of cathode materials obtained from nitrate precursors
According to EDX analysis the transition metal ratio is Ni/Co/Mn = 0.14/0.13/0.60
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Material Electrode
Effect of calcination time and temperature on particle size distribution of cathode materials obtained from nitrate precursors
Sample d10, μm d50, μm d90, μm
Preliminary 1.8 12.5 26.7
800°С, 5 h 6.1 19.0 38.4
800°С, 10 h 5.6 20.2 36.1
900°С, 8 h 3.7 19.5 41.7 9
Crystal structure of synthesized cathode materials
I003/I104 D, нм
1.23 112
0.78 72
0.42 57
0.59 65
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Results of electrochemical investigations
Discharge capacity after 100 cycles charge/discharge in voltage range 4.4-2.8V
Discharge curves before and after activation (From nitrate, 900°C, 8 hours of calcination
Sample Capacity, mAh/g 4.4-2.8V 4.8-2.8V 4.8-2.8V
From Nitrate, 900°C 8 h 160 (С/3) 225(С/3) 265(С/20) 175 (С/3) 250(С/4) –
From Acetate 900°C 8 h 105 (С/2) 170(С/4) – 11
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Thank you for your attention
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Ресурс при циклировании в диапазоне 4,4-2,8В относительно лития при скорости заряда и разряда С/3
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