Specification
CATHODE ACTIVE MATEMAH, FOR SECONDARY BATTERY
The present invention relates to a cathode active material for secondary
5 batteries. More specific:ally, the present invention relates to a cathode active material
for secondary batteries having long lifespan and superior storage propelties and exei-ting
superior safety based on a specific element composition.
(BACKGROUND ART^
Technological development and increased demand for mobile equipment have
10 led to a rapid increase in the demand for secondary batteries as energy sources.
Among these secondaty balteries, lithium secondary batteries having 11if:lr energy
density and voltage, long lifespan and low self-discharge are commercially available
-
aiid widely used.
111 addition, increased interest in enviroamental Issues has brought about a great
15 deal of research associated witli electric vehicles (EVs) and hybrid electric vehicles
(HEVs) as substitutes for vehicles using fossil fiaels such as gasoline vehicles and diesel
vehicles which are main factors of air pollution. Tliese electric vehicles generally use
nickel hydride metal mi-MH) secondary batteries as power sources of electric vehicles
(EVs), hybrid electric vehicles (HEVs) and the lilte. H-lowever, a great deal of study
associated with use of lithium secondasy batteries with high energy density and
discharge voltage is currently underway and some of them are commercially available.
5 In particular, lithium secondary batteries used for electric vehicles should have
high energy density, exhibit great power within a short time and be used under harsh
conditions for 10 years or longer, thus requiring considerably superior stability arid long
lifespan, as compared to conventional small lithium secondary batteries.
Conventional lithium secondary batteries generally utilize a lithium cobalt
10 composite oxide having a layered structure for a cathode and a graphite-based material
for ail anode. However, such lithium cobalt composite oxide is disadva~itageously
unsuitable for electric vehicles in terms of presence of ektremely expelisive cobalt as a
main element and low safety. Accordingly, lithium manganese composite oxide
having a spinel structure containing manganese that is cheap and has superior safety is
15 suitable h r use as a cathode of lithium ion secondary batteries for electric vehicles.
However, lithium manganese con~posite oxides cause deterioration in battery
properties since manganese is released into an electrolyte due to affection of the
electrolyte when stored at high temperature. Accordingly, there is a need for a solution
to this phenomenon. In addition, as compared to coiiventional lithiuni cobalt
coinposite oxide or lithium nickel composite oxide, lithium manganese composite
oxides have a disadva~itage of low capacity per unit weight, thus having a limitation of
an increase in capacity per battery weight. Lithium manganese composite oxide
should be used in combination with battery design capable of solving this phenomenon
5 in order to allow the same to be practically available as a power source of electric
vehicles.
In order to solve these disadvantages, layered mixed meis11 oxides,
LiNi,Mn,Co,O2 (x+ytz=l) and the like are used, but they cannot secure satisfactory
stability yet. Surface-treatment is attempted in order to solve this disadvantage, but
10 problems such as increase in price which is one of the most important problems in the
battery market such as electric vehicles occur due to the necessity of additional
processes.
~TECH- NIGALPR OBLEM]
15 Therefore, the present invention has been made to solve the above problems
and other technical problems t1ia.t have yet to be resolved.
As a result of a variety of extensive and intensive studies and experiments to
solve the problems a.s described above, the inventors of the present invention have
discovered that, when a cathode is produced using a cathode active material that ha.s a
specific element composition as shown in the compound of Formula 1 and includes a
transition metal layer containing lithium, and a secondary battery is fabricated based on
the cathode, lifespan can be greatly improved without using additional processes.
5 Based on this discovery, the present invention has been completed.
In accordance with one aspect of the present invention, provided is a cathode
active material for secondary batteries comprising a compound having a transition metal
layer containing lithium as at least one coinpound selected from tlie following Fosniula
10 1:
wliesein M is ari element stable for a six-coordination structure, which is at
least one selected from transition metals that belong to first and second period elements;
-4xy is satisfied iai a case of 3x-y.
l'lie cathode active material according to the preseiit invention exhibits
improved cycle propelties and storage properties of an active material, tluough
stabilization of crystal structure, based on the strong bonding force of P contained in the
elernent composition and variation in oxidation number by Li (lithium) present in tlie
5 transition metal layer.
When the content of P is excessively high, it inhibits crystallization of the
cathode active material arid it may be difficult to improve ~serformance 01' (Ire active
material. As defined above, the content is preferably lower than 0.1, more preferably
O
A battery was fabricated in the same manner as in Example 1 excep"chal a
cathode active material having a composition of x=O was synthesized.
5 A battery was fabricated in the same inanner as in Example 1 except that a
cathode active material having a composition of x=0.05 was synthesized.
A battery was fabricated in the same manner as in Example 1 except that a
cathode active material having a composition of x=0.005 was synthesized.
The batteries fabricated in Examples I to 4 and Comparative Example 1 were
charged and discharged at O.IC, capacities thereof were measured, and deterioration in
caps-city .with cycles was measured under charge and discharge conditions of 0.5C.
'The results thus obtained are shown in the following Table 1.
15 [TABLE 11
cycle capacity (%)
contain P as a different element other than a transition metal, they did not exhibit a great
Ex. 1
--
Comp. Ex. 1
Ex. 2
Ex. 3
Ex. 4
difference in capacity. As the content of P increased, the capacity there01 slightly
decreased, but was not significant.
As can be seen from Table 1 above, although the batteries of Examples 1 to 4
167
165
166
162
168
5 On the other hand, the batteries (Examples 1 to 4) using a cathode active
98.0
93.2.
-
98.3
98.1
97.2
inaterial containing P exhibited a considerably low capacity deterioration with an
increase in cycles, as compared to the battery (Comparative Example 1) using a cathode
active material containing no P. Specifically, for the 30'" cycle capacity to the 1'' cycle
capacity, the batteries of Examples 1 to 4 exhibited at least 4% or higher capacity, as
10 compared to the battery of Comparative Exaniple 1. This difference reached several
tens of % at 300 cycles or more, and as described above, batteries for vehicles are
charged 1000 cycles or more and under these conditions, the difference increases.
The batteries fabricated in Example 1 and Comparative Example 1 were
charged and discharged 5 and 25 cycles at 0.5C9 and discharge profiles at these cycles
are shown in Fig. 1.
As can be seen from Fig. 1, the battery of Example 1 exhibited deterioration at
5 the end stage of discharge, and in particular, a re~narltable decrease in voltage drop, as
compared to the battery of Comparative Example 1. This means that deterioration is
decreased due to structural change of the cathode. Such deterioration at thc c11d stage
of discharge is the most impostant factor that rapidly deteriorates the power of batteries
for electric, vehicles or hybrid electric vehicles and the Iactor is more important than a
10 decreased capacity that can be measured in general batteries.
In this regard, the cathode active material of the present invention can
considerably redlnce deterioration at the end stage of discharge. As can be seen from
Fig. 1, such a phenomenon becomes serious, as the number of cycles increases. That
is, the deterioration difference at the end stage of discharge at the 25''' cycle is greater
15 than thatat the 5"' cycle.
Batteries for vehicles require 3600 cycles or more of charge and discharge
although they are charged and discharged only once a day under product guarantee
conditions of 10 years or longer, thus making this difference considerably great.
Accordingly, small difference in small conventional batteries fu~ther increases in
batteries for vehicles, and difference in cycle properties, variation in charge and
discharge profiles and the like are more irnpo~tanth an the small difference in capacity.
Although the preferred embodiments of the present invention have been
disclosed for illustrative purposes, those slcilled in the art will appreciate that various
5 modifications, additions and substitutions are possible, without departing fiom the
scope and spirit of the invention as disclosed in the accompanying claims.
As apparent from the afore-going, the cathode active material according to the
present invention can improve lifespan properties based on a specific elenient
10 composition, and in particular, is thus preferably useful for devices requiring use for a
long period of time due to superior cycle properties.
Claims:
[claim 1 A cathode active material for seconldary batteries comprising a
compound having a transition metal layer containing lithium as at least one compound
selected from the following Formula 1 :
wherein M is an element stable for a six-coordination stmcture, ~vlrich is at
least one selected from transition metals that belong to the first and second period
elements;
-4xy is satisfied in a case of 3x-y
--
[claim 2 The cathode active material according to claim 1, wherein the content
of P satisfies the condition of 0
Documents
Application Documents
| # |
Name |
Date |
| 1 |
9308-DELNP-2012-Form-18-(01-11-2012).pdf |
2012-11-01 |
| 2 |
9308-DELNP-2012-Correspondence-Others-(01-11-2012).pdf |
2012-11-01 |
| 3 |
Power of Authority.pdf |
2012-11-05 |
| 6 |
Form-1.pdf |
2012-11-05 |
| 7 |
Drawings.pdf |
2012-11-05 |
| 8 |
9308-DELNP-2012-Proof of Right (MANDATORY) [27-07-2018(online)].pdf |
2018-07-27 |
| 9 |
9308-DELNP-2012-PETITION UNDER RULE 137 [27-07-2018(online)].pdf |
2018-07-27 |
| 10 |
9308-DELNP-2012-OTHERS-300718.pdf |
2018-07-31 |
| 11 |
9308-DELNP-2012-Correspondence-300718.pdf |
2018-07-31 |
| 12 |
9308-DELNP-2012-OTHERS-300718..pdf |
2018-08-11 |
| 13 |
9308-Delnp-2012-Letter To Atomic Energy-(13-03-2020).pdf |
2020-03-13 |
| 14 |
9308-DELNP-2012-FER.pdf |
2021-10-17 |
| 15 |
9308-DELNP-2012-PETITION UNDER RULE 137 [15-03-2022(online)].pdf |
2022-03-15 |
| 16 |
9308-DELNP-2012-OTHERS [15-03-2022(online)].pdf |
2022-03-15 |
| 17 |
9308-DELNP-2012-FORM-26 [15-03-2022(online)].pdf |
2022-03-15 |
| 18 |
9308-DELNP-2012-FER_SER_REPLY [15-03-2022(online)].pdf |
2022-03-15 |
| 19 |
9308-DELNP-2012-DRAWING [15-03-2022(online)].pdf |
2022-03-15 |
| 20 |
9308-DELNP-2012-CORRESPONDENCE [15-03-2022(online)].pdf |
2022-03-15 |
| 21 |
9308-DELNP-2012-CLAIMS [15-03-2022(online)].pdf |
2022-03-15 |
| 22 |
9308-DELNP-2012-ABSTRACT [15-03-2022(online)].pdf |
2022-03-15 |
| 23 |
9308-DELNP-2012- LETTER TO DAE ( REMINDER-I )- (25-03-2022).pdf |
2022-03-25 |
| 24 |
9308-DELNP-2012-Response to office action [19-07-2022(online)].pdf |
2022-07-19 |
| 25 |
9308-DELNP-2012-Annexure [19-07-2022(online)].pdf |
2022-07-19 |
| 26 |
9308-DELNP-2012-Response to office action [20-07-2022(online)].pdf |
2022-07-20 |
| 27 |
9308-DELNP-2012-Annexure [20-07-2022(online)].pdf |
2022-07-20 |
| 28 |
9308-DELNP-2012-PA [14-11-2022(online)].pdf |
2022-11-14 |
| 29 |
9308-DELNP-2012-Description.pdf |
2022-11-14 |
| 30 |
9308-DELNP-2012-AtomicEnergy-14-11-2022.pdf |
2022-11-14 |
| 31 |
9308-DELNP-2012-ASSIGNMENT DOCUMENTS [14-11-2022(online)].pdf |
2022-11-14 |
| 32 |
9308-DELNP-2012-8(i)-Substitution-Change Of Applicant - Form 6 [14-11-2022(online)].pdf |
2022-11-14 |
| 33 |
9308-DELNP-2012-Response to office action [21-11-2022(online)].pdf |
2022-11-21 |
| 34 |
9308-DELNP-2012-AtomicEnergy-01-05-2024.pdf |
2024-05-01 |
| 35 |
9308-DELNP-2012-Response to office action [15-04-2025(online)].pdf |
2025-04-15 |
| 36 |
9308-DELNP-2012-REPLY FROM DAE-18-06-2025.pdf |
2025-06-18 |
| 37 |
9308-DELNP-2012-Response to office action [09-04-2026(online)].pdf |
2026-04-09 |
Search Strategy
| 1 |
9308delnp2012E_21-09-2021.pdf |