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 yury.koshtyal@gmail.com

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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

4

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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