Title of Invention	AN IMPROVED PROCESS FOR THE SYNTHESIS OF LITHIUM ALUMINIUM NICKELATE (LIAT0.5 Ni0.5 O2) CATHODE MATERIAL USEFUL FOR THE ROCKING CHAIR LlTHIUM ION CELLS
Abstract	An improved process for the synthesis of lithium aluminium nickelate (LIA10.5 Ni0.5 O2) cathode material useful for the rocking chair lithium ion cells The invention relates to the preparation of lithium aluminium nickelate (LIAI0.5 Ni0.5 02) a composite, which is very useful for high voltage lithium reversible cells and can be prepared by mixing oxides of aluminium, nickel with lithium hydroxide by heating together all in solid state condition. LIA10.5 Ni0.5 O2 is a reversible cathode material useful for high voltage cells of lithium in no aqueous media.

Title of Invention

AN IMPROVED PROCESS FOR THE SYNTHESIS OF LITHIUM ALUMINIUM NICKELATE (LIAT0.5 Ni0.5 O2) CATHODE MATERIAL USEFUL FOR THE ROCKING CHAIR LlTHIUM ION CELLS

Abstract

An improved process for the synthesis of lithium aluminium nickelate (LIA10.5 Ni0.5 O2) cathode material useful for the rocking chair lithium ion cells The invention relates to the preparation of lithium aluminium nickelate (LIAI0.5 Ni0.5 02) a composite, which is very useful for high voltage lithium reversible cells and can be prepared by mixing oxides of aluminium, nickel with lithium hydroxide by heating together all in solid state condition. LIA10.5 Ni0.5 O2 is a reversible cathode material useful for high voltage cells of lithium in no aqueous media.

Full Text	This invention relates to a process for the synthesis of lithium aluminium nickelate (LIAI0.5 Ni0.5 O2) cathode material useful for the rocking chair lithium ion cells The invention particularly relates to the preparation of lithium aluminium nickelate (LIA10.5 Ni0.5 O2) a composite, which is very useful for high voltage lithium reversible cells and can be prepared by mixing oxides of aluminium, nickel with lithium hydroxide by heating together all in solid state condition. LIA10.5 Ni0.5 O2 is a reversible cathode material useful for high voltage cells of lithium in no aqueous media. LIA10.5 Ni0.5 O2 compound is hexagonal material is well known from 1995 as a good battery cathode for reversibility in non-aqueous solutions. LiAh/4 Ni3/4 O2 can be prepared by heating a pressed mixture of LiNO3, AI(OH)3 and 2NiCO3 3Ni(OH)2 in stochiometric proportion at 750°C for 24 hrs in air [S.I. Pyun, J.Power Source, 81 - 82 (1999)442]. In a recent paper LiAlyNh.y O2 was obtain by co-precipitation and freeze drying technique, in which an aqueous solutions of Al (NO3)3, Ni(NO3)2 and LiNO3 were mixed together. Then the obtained precursors were fired for 2 hrs at 700 - 800°C in air or oxygen [ Y.I.Jang, B.Huang, H.Wang, G R Maskaly and H. Tamura, J. Power source, 81 - 82 (1999) 589]. In all the above procedures available in the literature some disadvantages were observed. They are as follows: Phase impurity Longer duration of thermal preparation High temperature of operation pH control Several steps of preparation The main object of this present invention in to formulate a new procedure for the synthesis of LIA10.5 Ni0.5 O2 cathode material for the rocking chair lithium ion cells which obviate the draw backs of the hither to known methods. Further object of this invention in cyclability of the system by introducing aluminium in lithium nickelate compound & their by ensuring better reconsibility & partially replacing nickel also. Still another object is to use glycerol as binding agent to make an uniform homogenous mixture which permits uniform reaction to occur without any side reaction . Yet another object to this invention is to prepare lithium aluminium nicklate with oxides of nickel, aluminium & hydroxide of lithium. According the present invention relates to an improved process for the synthesis of lithium aluminium nickelate (LIA10.5 Ni0.5 O2) cathode material useful for the rocking chair lithium ion cells which comprises of heating hydroxides of lithium with oxides of nickel & aluminium in the molar ratio of 1: 0.5 : 0.5 respectively in the form of paste with glycerol and urea at temperatures initially at 200°C , subsequently kept at 800°C for 12 hours, cooling the resultant to room temperature to get lithium aluminium nickelate cathode material. In one of the embodiment of this invention the molar ratio of Li: Ni: Al is an 1 : The temperature of preparation of this compound in between 600°C to 800°C. In yet another embodiment of this invention glycerol is used as a binding agent for uniform product formation. This prevents any side reactions & partial reactions. A novel method of preparing this compound viz., LiAl0.5 Ni0.5 64 was carried out by uniform mixing of oxides of Al and Ni with LiOH and this mixture was made into a paste by adding necessary quantity of glycerol and the paste was calcined at 750°C continuously for 12 hrs in a furnace. The prepared product was subjected to x-ray analysis. The product was found to be in single phase. The present invention, describes the method of synthesis of cathode material for a secondary battery, by heating a paste prepared by mixing fine particles of LiOH, Al2O3 and NiO in glycerol. This paste was initially heated slowly in a furnace to evaporate off glycerol in order to get a dried mass at 250°C. This dried mass was then continuously heated to 800°C for 12 hrs. The compound formed was slowly cooled to room temperature and was ground well and then examined for its particles size, colour and XRD exposure. It was found that the prepared sample was black in colour and was homogenous, X-rays analysis confirmed the formation of LiAlo.s Ni0.5 O2 according to Fig. 1. The novelty of this process is use of finding agent glycerol and flux therefore The process given pure product and leaves behind no unreacted components. The process does not produce partial reactions. The time takes for normal preparation of the product is much less than other know methods. Single unit procedures compared to other methods. The following examples are given by the way of illustration and should not be construed the scope of this invention. The following examples give the way of synthesizing LiAl0.5 N10.5O2 Examples -1 Components LiOH 0.839 gm NiO 0.797 gm A12O3 0.510gm Flux (urea) 2.402 gm Binder (Glycerol) 2 ml Temperature 800°C Duration of heating 12 hrs Colour of the product Black Efficiency of the product 90% Phase Single Single electrode potential of LiAl0.5Ni0.5O2 w.r.t. in 1M LiC104 3.00v In propylene carbonate Examples - 2 Components LiOH 0.839 gm NiO 0.797 gm A12O3 0.510gm Flux (urea) 2.402 gm Binder (Glycerol) 2 ml Temperature 800°C Duration of heating 12hrs Colour of the product Black Efficiency of the product 90% Phase Single Single electrode potential of LiAl0.5Ni0.5O2 w.r.t. in 1M LiClO4 3.00v In propylene carbonate Hydroxide of lithium and oxides of nickel and were ground well to a fine powder in a pestle & motar arrangement. Glycerol was slowly added & then the mixture was ground well to form a paste. The paste was transferred in to a silica porcelain / crucible. The contract was slowly heated to 200°C initially & finally to 800°C for 12 hours. The product formed after the reaction was looked to ambient temperature & was ground well. The fine power was x-rayed to confirm the identity of the product & purity The following advantages are claimed in this invention for the preparation of lithium aluminium nickelate. A uniform homogeneous mixture of the ground compounds viz., oxides of aluminium and nickel with LiOH were made into a paste to get a product of high purity. Glycerol was used as a solvent for binding the oxides viz., aluminium and nickel with LiOH for making a paste of required consistency. The addition of glycerol enhanced the product of fine particles. The addition of flux (urea) / excess addition of glycerol (solvent) as a binding material for oxides does not change the colour or quality of the end product. We Claim: 1. An improved process for the synthesis of lithium aluminium nickelate (LIA10.5 Ni0.5 O2) cathode material useful for the rocking chair lithium ion cells which comprises of heating hydroxides of lithium with oxides of nickel & aluminium in the molar ratio of 1: 0.5 : 0.5 respectively in the form of paste with glycerol and urea at temperatures initially at 200°C , subsequently kept at 800°C for 12 hours, cooling the resultant to room temperature to get lithium aluminium nickelate cathode material. 2. A process as claimed in claims 1 wherein heating is carried in a furnace slowly up to 250°C to get the dried mass followed by heating at 800°Cfor12hrs. 3. A process as claimed in claims 1-2 wherein fine particles of the reactants viz LiOH, AI2Cl3 and NiO are bound by glycerol and made the mixture into a paste for uniform reaction during heating. 4. A process as claimed in claims 1 - 3 glycerol is used as a binder for the inorganic solid state reactants. 6. An improved process for the synthesis of lithium aluminium nickelate (LIA10.5 Ni0.5 O2) cathode material useful for the rocking chair lithium ion cells substantially as herein described with reference to the examples and drawing accompanying the specification.

Full Text

This invention relates to a process for the synthesis of lithium aluminium nickelate (LIAI0.5 Ni0.5 O2) cathode material useful for the rocking chair lithium ion cells
The invention particularly relates to the preparation of lithium aluminium nickelate (LIA10.5 Ni0.5 O2) a composite, which is very useful for high voltage lithium reversible cells and can be prepared by mixing oxides of aluminium, nickel with lithium hydroxide by heating together all in solid state condition. LIA10.5 Ni0.5 O2 is a reversible cathode material useful for high voltage cells of lithium in no aqueous media.
LIA10.5 Ni0.5 O2 compound is hexagonal material is well known from 1995 as a good battery cathode for reversibility in non-aqueous solutions. LiAh/4 Ni3/4 O2 can be prepared by heating a pressed mixture of LiNO3, AI(OH)3 and 2NiCO3 3Ni(OH)2 in stochiometric proportion at 750°C for 24 hrs in air [S.I. Pyun, J.Power Source, 81 - 82 (1999)442].
In a recent paper LiAlyNh.y O2 was obtain by co-precipitation and freeze drying technique, in which an aqueous solutions of Al (NO3)3, Ni(NO3)2 and LiNO3 were mixed together. Then the obtained precursors were fired for 2 hrs at 700 - 800°C in air or oxygen [ Y.I.Jang, B.Huang, H.Wang, G R Maskaly and H. Tamura, J. Power source, 81 - 82 (1999) 589].
In all the above procedures available in the literature some disadvantages were observed. They are as follows:
Phase impurity
Longer duration of thermal preparation
High temperature of operation
pH control
Several steps of preparation
The main object of this present invention in to formulate a new procedure for the synthesis of LIA10.5 Ni0.5 O2 cathode material for the rocking chair lithium ion cells which obviate the draw backs of the hither to known methods. Further object of this invention in cyclability of the system by introducing aluminium in lithium nickelate compound & their by ensuring better reconsibility & partially replacing nickel also.
Still another object is to use glycerol as binding agent to make an uniform homogenous mixture which permits uniform reaction to occur without any side reaction .
Yet another object to this invention is to prepare lithium aluminium nicklate with oxides of nickel, aluminium & hydroxide of lithium.
According the present invention relates to an improved process for the synthesis of lithium aluminium nickelate (LIA10.5 Ni0.5 O2) cathode material useful for the rocking chair lithium ion cells which comprises of heating hydroxides of lithium with oxides of nickel & aluminium in the molar ratio of 1: 0.5 : 0.5 respectively in the form of paste with glycerol and urea at temperatures initially at 200°C , subsequently kept at 800°C for 12 hours, cooling the resultant to room temperature to get lithium aluminium nickelate cathode material.
In one of the embodiment of this invention the molar ratio of Li: Ni: Al is an 1 :
The temperature of preparation of this compound in between 600°C to 800°C. In yet another embodiment of this invention glycerol is used as a binding agent for uniform product formation. This prevents any side reactions & partial reactions.
A novel method of preparing this compound viz., LiAl0.5 Ni0.5 64 was carried out by uniform mixing of oxides of Al and Ni with LiOH and this mixture was made into a paste by adding necessary quantity of glycerol and the paste was calcined at 750°C continuously for 12 hrs in a furnace. The prepared product was subjected to x-ray analysis. The product was found to be in single phase.
The present invention, describes the method of synthesis of cathode material for a secondary battery, by heating a paste prepared by mixing fine particles of LiOH, Al2O3 and NiO in glycerol. This paste was initially heated slowly in a furnace to evaporate off glycerol in order to get a dried mass at 250°C. This dried mass was then continuously heated to 800°C for 12 hrs. The compound formed was slowly cooled to room temperature and was ground well and then examined for its particles size, colour and XRD exposure. It was found that the prepared sample was black in colour and was homogenous, X-rays analysis confirmed the formation of LiAlo.s Ni0.5 O2 according to Fig. 1. The novelty of this process is use of finding agent glycerol and flux therefore
The process given pure product and leaves behind no unreacted components. The process does not produce partial reactions.
The time takes for normal preparation of the product is much less than other know methods.
Single unit procedures compared to other methods.
The following examples are given by the way of illustration and should not be construed the scope of this invention.
The following examples give the way of synthesizing LiAl0.5 N10.5O2
Examples -1 Components
LiOH 0.839 gm
NiO 0.797 gm
A12O3 0.510gm
Flux (urea) 2.402 gm
Binder (Glycerol) 2 ml
Temperature 800°C
Duration of heating 12 hrs
Colour of the product Black
Efficiency of the product 90%
Phase Single
Single electrode potential of
LiAl0.5Ni0.5O2 w.r.t. in 1M LiC104 3.00v
In propylene carbonate
Examples - 2 Components
LiOH 0.839 gm
NiO 0.797 gm
A12O3 0.510gm
Flux (urea) 2.402 gm
Binder (Glycerol) 2 ml
Temperature 800°C
Duration of heating 12hrs
Colour of the product Black
Efficiency of the product 90%
Phase Single
Single electrode potential of
LiAl0.5Ni0.5O2 w.r.t. in 1M LiClO4 3.00v
In propylene carbonate
Hydroxide of lithium and oxides of nickel and were ground well to a fine powder in a pestle & motar arrangement. Glycerol was slowly added & then the mixture was ground well to form a paste. The paste was transferred in to a silica porcelain / crucible.
The contract was slowly heated to 200°C initially & finally to 800°C for 12 hours. The product formed after the reaction was looked to ambient temperature & was ground well. The fine power was x-rayed to confirm the identity of the product & purity
The following advantages are claimed in this invention for the preparation of lithium aluminium nickelate.
A uniform homogeneous mixture of the ground compounds viz., oxides of aluminium and nickel with LiOH were made into a paste to get a product of high purity.
Glycerol was used as a solvent for binding the oxides viz., aluminium and nickel with LiOH for making a paste of required consistency. The addition of glycerol enhanced the product of fine particles.
The addition of flux (urea) / excess addition of glycerol (solvent) as a binding material for oxides does not change the colour or quality of the end product.

We Claim:
1. An improved process for the synthesis of lithium aluminium nickelate
(LIA10.5 Ni0.5 O2) cathode material useful for the rocking chair lithium
ion cells which comprises of heating hydroxides of lithium with oxides
of nickel & aluminium in the molar ratio of 1: 0.5 : 0.5 respectively in
the form of paste with glycerol and urea at temperatures initially at
200°C , subsequently kept at 800°C for 12 hours, cooling the resultant
to room temperature to get lithium aluminium nickelate cathode
material.
2. A process as claimed in claims 1 wherein heating is carried in a
furnace slowly up to 250°C to get the dried mass followed by heating at
800°Cfor12hrs.
3. A process as claimed in claims 1-2 wherein fine particles of the
reactants viz LiOH, AI2Cl3 and NiO are bound by glycerol and made the
mixture into a paste for uniform reaction during heating.
4. A process as claimed in claims 1 - 3 glycerol is used as a binder for
the inorganic solid state reactants.
6. An improved process for the synthesis of lithium aluminium nickelate (LIA10.5 Ni0.5 O2) cathode material useful for the rocking chair lithium ion cells substantially as herein described with reference to the examples and drawing accompanying the specification.

Documents:

348-DEL-2001-Abstract.pdf

348-DEL-2001-Claims.pdf

348-del-2001-correspondence-others.pdf

348-del-2001-correspondence-po.pdf

348-DEL-2001-Description (Complete).pdf

348-DEL-2001-Drawings.pdf

348-DEL-2001-Form-1.pdf

348-del-2001-form-18.pdf

348-DEL-2001-Form-2.pdf

348-del-2001-form-3.pdf

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Patent Number

231661

Indian Patent Application Number

348/DEL/2001

PG Journal Number

13/2009

Publication Date

27-Mar-2009

Grant Date

07-Mar-2009

Date of Filing

27-Mar-2001

Name of Patentee

COUNCIL OF SCIENTIFIC AND INDUSTRIAL RESEARCH

Applicant Address

RAFI MARG, NEW DELHI-110 001, INDIA.

Inventors:

#	Inventor's Name	Inventor's Address
1	THIAGARAJAN VASUDEVAN	PROF. & HEAD,ALAGAPPA UNIVERSITY, KARAIKUDY ,630003, INDIA.
2	ANGAIAH SUBRAMANIAN	INUSTRIAL CHEMISTRY ALAGAPPA UNIVERSITY, KARAIKUDY ,630003, INDIA.
3	ARIYANAN MANI	SCIENTIST, CECRI, KARAIKUDY ,630003, INDIA.
4	RAMAIYER GANGADHARAN	EMERITUS SCIENTIST, ALAGAPPA UNIVERSITY, KARAIKUDY ,630003, INDIA.

PCT International Classification Number

H01M 4/02

PCT International Application Number

N/A

PCT International Filing date

PCT Conventions:

#	PCT Application Number	Date of Convention	Priority Country
1			NA