Specification
High voltage negative active material for a rechargeable lithium battery
The invention relates to active material for the negative electrode of secondary
rechargeable lithium batteries, wherein the active material is based on doped
or undoped carbon-bearing lithium titanium ramsdellite oxide with general
formula Li2Ti3O7 or Li2.28Ti3.43O8
Anode materials for rechargeable lithium batteries are generally selected from
the carbon group. Carbon materials might have security issues in extreme
conditions. First, while charging at very fast rates and/or at low temperature,
Li can deposit at the surface of carbon and hence the formation of lithium
dendrites can induce soft short. Second, abusive overheating induces the
dissolution of the passivation layer made of the reduction products of
electrolyte's solvents at the potential of graphite; and the resulting continuous
reduction of solvents can be a first step to thermal run away.
Numerous efforts have been made to find alternative electrochemical active
anode materials to replace graphite. Notably, lithium titanium oxides, such as
the spinel phase Li4Ti5O12 as related in Journal of Electrochemical Society 141
(1994) L147, or the ramsdellite phase Li2Ti3O7 as reported in Material Research
Bulletin 32 (1997) 993, have been proposed due to several advantages versus
carbon: i.e. a higher average voltage around 1.5V vs. Li, improving the security
while cycling, a low irreversible loss and a lower polarization. The spinel
structure inserts lithium in a two-phase process due to the spinel to rocksalt
phase transition, presenting a 1.55V vs. Li plateau, and acquiring a maximum
capacity of 175 Ah/kg, whilst the ramsdellite inserts lithium topotactically in a
solid solution with a flat S-shape charge-discharge curve corresponding to a
one-phase process at a voltage range of 1-2V vs Li.
Lithium titanate oxide (Li2Ti3O7) is regarded as promising negative electrode
material because of the low cost of production, and the non-toxicity of
CONFIRMATION COPY
titanium. While the theoretical capacity is 198 Ah/kg, in practice the reversible
capacities are between 120 and 130 Ah/kg for low current densities (C/15) and
attain only 110 Ah/kg at higher current densities (C). As a consequence the
reversible capacity, the polarisation observed upon lithium insertion and the
required high temperature for the firing process strongly limit the application
field of this compound.
A lower synthesis temperature and better cyclability at low current density can
be achieved by substitution of a small amount of Ti4+ by Fe3+ in Li2Ti3O7, using a
ceramic route. However, the first discharge curve shows a plateau due to the
transformation Fe3+/Fe2+, which limits the reversible capacity, and the other
performances are not improved, compared with Li2Ti3O7. According to
EP1623473 B1, the reversible capacity can be improved to 140 Ah/kg when the
lithium titanium oxide having the ramsdellite structure, according to the
general formula Li2+vTi3-wFexMyM'zO7. α, is co-substituted with one or two of the
following elements: Ti3+, Co2+, Co3+, Ni2+, Ni3+ Cu2+, Mg2+, Al3+, In3+, Sn4+, Sb3+,
Sb5+ Substituted materials are obtained at lowered synthesis temperatures,
which decreases the production cost.
Furthermore, according to PCT/EP2008/009763, when the active material
contains a carbon richer phase with general formula
Li2+v-4cCcTi3.wFexMyM,zO7-α, and containing two of the following elements: Ti3+,
Co2+, Co3+, Ni2+, Ni3+ Cu2+, Mg2+, Al3+, ln3+, Sn4+, Sb3+, Sb5+, the specific reversible
capacity is increased to 190 Ah/kg, close to the theoretical value of the
ramsdellite lithium titanate . The electrochemical results show an
electrochemical curve having a two-step voltage profile, one between 2.2 and
1.6 V and the second under 1.5 V. The material was obtained by grinding and
mixing a lithium, titanium and iron compound, a C precursor compound, and a
M and M' compound, followed by a sintering process at elevated temperature in
a neutral atmosphere.
It is an object of the present invention to further improve the performances in
terms of high energy and high specific power, whilst respecting the safety of
use and the environment, all of this at a reasonable cost.
This is obtained by a composite negative active material for a lithium battery,
comprising a carbon substituted ramsdellite phase having a general formula
Li2-4cCcTi3O7, with 0.1 < c < 0.5, and a spinel phase having a general formula
Li1+xTi2-xO4 with 0 0; x+y+z = w and 0 < w < 0.3; 0.1 < c < (2+v)/4,
and a is related to the formal oxidation numbers n and n' of M and M' by the
relation 2a = -v+4w-3x-ny-n'z, where n and n' are the formal oxidation numbers
of M and M' respectively.
Preferably M and M' are different metals selected from the list consisting of
Ti3+, Co2+ Co3t, Ni2+, Ni3+, Cu2+, Mg2+, Al3+, ln3+, Sn4+, Sb3+, Sb5+; and preferably
M= Ni2+ and M' = Al3+
The active material described above preferably has a carbon content of 1.0 to
1.5 wt%. Also preferred is a spinel content between 5 and 16 mole%, and even
between 8 and 11 mole%.
The invention also covers a secondary rechargeable battery having an anode
material described before.
The negative active electrode material according to the invention is constituted
of a composite material containing principally the undoped or doped C-bearing
Li2Ti307 ramsdellite phase and a second phase of spinel type Li1-xTi2-XO4, with
0 0.8 %wt, is compensated by
the formation of the lithium rich spinel phase Li4Ti50i2 or LiVxTi2x04 0 0; x+y+z = w and 0 < w < 0.3;
0.1 < c < (2+v)/4; and a is related to the formal oxidation numbers n and n' of M
and M' by the relation 2a = -v+4w-3x-ny-n'z, where n and n' are the formal
oxidation numbers of M and M' respectively.
3. The active material of claim 2, wherein M and M' are different metals
selected from the list consisting of Ti3+ Coz+, Co3+, Ni2+, Ni3+, Cu2+, Mg2+, Al3+
ln3+, Sn4+, Sb3+, Sb5+; and preferably M= Ni2+ and M' = Al3+
4. The active material of any one of claims 1 to 3, having a carbon content of
1.0 to 1.5 wt%.
5. The active material of any one of claims 1 to 4, having a spinel content
between 5 and 16 mole%, and preferably between 8 and 11 mole%.
6. The composite negative active material according to claim 1, comprising at
least 99 mole%, and preferably at least 99.9 mole% of both of said carbon
substituted ramsdellite phase having a general formula Li2.4cCcTi3O7 and said
spinel phase having a general formula Li1+xTi2-xO4 with 0
Documents
Application Documents
| # |
Name |
Date |
| 1 |
3468-KOLNP-2011-AbandonedLetter.pdf |
2018-10-04 |
| 1 |
ABSTRACT-3468-KOLNP-2011.jpg |
2011-10-07 |
| 2 |
3468-KOLNP-2011-FER.pdf |
2017-06-13 |
| 2 |
3468-KOLNP-2011-SPECIFICATION.pdf |
2011-10-07 |
| 3 |
3468-KOLNP-2011-PCT REQUEST FORM.pdf |
2011-10-07 |
| 3 |
3468-KOLNP-2011-(15-02-2012)-ASSIGNMENT.pdf |
2012-02-15 |
| 4 |
3468-KOLNP-2011-PCT PRIORITY DOCUMENT NOTIFICATION.pdf |
2011-10-07 |
| 4 |
3468-KOLNP-2011-(15-02-2012)-CERTIFIED COPIES(OTHER COUNTRIES).pdf |
2012-02-15 |
| 5 |
3468-KOLNP-2011-INTERNATIONAL PUBLICATION.pdf |
2011-10-07 |
| 5 |
3468-KOLNP-2011-(15-02-2012)-CORRESPONDENCE.pdf |
2012-02-15 |
| 6 |
3468-KOLNP-2011-GPA.pdf |
2011-10-07 |
| 6 |
3468-KOLNP-2011-(15-02-2012)-FORM 3.pdf |
2012-02-15 |
| 7 |
3468-KOLNP-2011-FORM-5.pdf |
2011-10-07 |
| 7 |
3468-KOLNP-2011-(15-02-2012)-PA.pdf |
2012-02-15 |
| 8 |
3468-KOLNP-2011-FORM-3.pdf |
2011-10-07 |
| 8 |
3468-KOLNP-2011-FORM 18.pdf |
2011-10-25 |
| 9 |
3468-KOLNP-2011-ABSTRACT.pdf |
2011-10-07 |
| 9 |
3468-KOLNP-2011-FORM-2.pdf |
2011-10-07 |
| 10 |
3468-KOLNP-2011-CLAIMS.pdf |
2011-10-07 |
| 10 |
3468-KOLNP-2011-FORM-13.pdf |
2011-10-07 |
| 11 |
3468-KOLNP-2011-CORRESPONDENCE.pdf |
2011-10-07 |
| 11 |
3468-KOLNP-2011-FORM-1.pdf |
2011-10-07 |
| 12 |
3468-KOLNP-2011-DESCRIPTION (COMPLETE).pdf |
2011-10-07 |
| 12 |
3468-KOLNP-2011-DRAWINGS.pdf |
2011-10-07 |
| 13 |
3468-KOLNP-2011-DESCRIPTION (COMPLETE).pdf |
2011-10-07 |
| 13 |
3468-KOLNP-2011-DRAWINGS.pdf |
2011-10-07 |
| 14 |
3468-KOLNP-2011-CORRESPONDENCE.pdf |
2011-10-07 |
| 14 |
3468-KOLNP-2011-FORM-1.pdf |
2011-10-07 |
| 15 |
3468-KOLNP-2011-CLAIMS.pdf |
2011-10-07 |
| 15 |
3468-KOLNP-2011-FORM-13.pdf |
2011-10-07 |
| 16 |
3468-KOLNP-2011-ABSTRACT.pdf |
2011-10-07 |
| 16 |
3468-KOLNP-2011-FORM-2.pdf |
2011-10-07 |
| 17 |
3468-KOLNP-2011-FORM-3.pdf |
2011-10-07 |
| 17 |
3468-KOLNP-2011-FORM 18.pdf |
2011-10-25 |
| 18 |
3468-KOLNP-2011-FORM-5.pdf |
2011-10-07 |
| 18 |
3468-KOLNP-2011-(15-02-2012)-PA.pdf |
2012-02-15 |
| 19 |
3468-KOLNP-2011-GPA.pdf |
2011-10-07 |
| 19 |
3468-KOLNP-2011-(15-02-2012)-FORM 3.pdf |
2012-02-15 |
| 20 |
3468-KOLNP-2011-INTERNATIONAL PUBLICATION.pdf |
2011-10-07 |
| 20 |
3468-KOLNP-2011-(15-02-2012)-CORRESPONDENCE.pdf |
2012-02-15 |
| 21 |
3468-KOLNP-2011-PCT PRIORITY DOCUMENT NOTIFICATION.pdf |
2011-10-07 |
| 21 |
3468-KOLNP-2011-(15-02-2012)-CERTIFIED COPIES(OTHER COUNTRIES).pdf |
2012-02-15 |
| 22 |
3468-KOLNP-2011-PCT REQUEST FORM.pdf |
2011-10-07 |
| 22 |
3468-KOLNP-2011-(15-02-2012)-ASSIGNMENT.pdf |
2012-02-15 |
| 23 |
3468-KOLNP-2011-SPECIFICATION.pdf |
2011-10-07 |
| 23 |
3468-KOLNP-2011-FER.pdf |
2017-06-13 |
| 24 |
ABSTRACT-3468-KOLNP-2011.jpg |
2011-10-07 |
| 24 |
3468-KOLNP-2011-AbandonedLetter.pdf |
2018-10-04 |
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