Report LTO Anode MaterialSample - MarketResearch · LTO-based Anode Technology Transfer Cases...

January, 2013

LIB Key Patent Analysis: LTO Anode Material

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JAN, 2013

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Table of Contents

1. Introduction Patent Analysis Background

Patent Analysis Scope

Patent Analysis Method

2. Technology Overview

Overview of Anode Technology

Overview of Lithium Titan Oxide (Li₄Ti₅O₁₂)

Anode Material Technology Development Trend

3. Patent Application Trend Analysis

Technology Classification

Patent Search Results and Selection of Validated

Patents

Patent Application Trend by Country/Year

Major Patent Applicants by Country

TOP10 Patent Applicants

Patent Application Trend by Technology

Patent Application Trend by Technology/Year

Patent Application Trend by

Technology/Applicant

Technology Status by Period of Application

4. Key Patent Analysis

Key Patent Analysis Overview

- Key Patent Selection Method

- Key Patent Selection Status

- Key Patent Application Distribution by Year

- Key Patent Application Distribution by

Applicant/Technology

- Key Patent Status of Major Applicants by

Technology

- Key Patent Status by Company

- Key Patent Technology Flowchart

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Concentrated Patent Technology by Country

Patent Application Distribution of Major

Applicants by Technology

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Table of Contents

※Appendix :

List of Validated Patents on LTO-based Anode Material

(Sold Separately)

7. Technology to Overcome LTO limitations

Sanyo: Development of MoOx Anode

Sanyo: MoOx Anode Patent Application Status

Technology Transfer Trend of Research

Institute/University

LTO-based Anode Technology Transfer Cases

Patent Dispute Trend

6. LIB Technology Transfer & Patent Dispute Trends

8. Conclusion/Implication

LTO-based Anode Patent Trend

Major LTO-based Anode Company Trend

Patent Technologies in Issue

Implications

5. Key Patent In-depth Analysis

Key Patent Citation Analysis

Patented Technology Applications

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Key Patent Analysis by Major Companies

- Toshiba

- Medtronic

- Toho Titanium

- Altairnano

- Panasonic

- CEA

- LG Chemical

- EnderDel

- Hydro-Quebec

- Sanyo / GS Yuasa

- SUD-Chemie

- Others

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Introduction

Patent Analysis Background

Patent Analysis Scope


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Patent Analysis BackgroundFossil fuel society is a politically unstable society that rely on local crude oil which is a depleting energy source with high risk and

which emits green gas and pollutants that have negative impact on climate and environment. In order to realize a sustainable society,

new solutions are continuously being sought to solve the problem that fossil fuel cause.

The most realistic way to solve the problem of fossil fuel is to commercialize high capacity power storage technology, popularize the

use of electrical vehicles and store power energy to be used whenever in need.

Every year billions of lithium-ion secondary batteries are being produced to be used in portable electric devices and power tools such

as mobile phone and notebook PC. Today’s lithium-ion batteries produced mainly using carbon/organic electrolyte/LiCoO₂ faces many

challenges to be used for vehicles and as a result, there is requirement to resolve the price, cycle life, stability, reliability and

sustainability problems. In particular for batteries used in vehicles which charging time is of great importance, development of rapid

charging batteries is becoming a big issue.

SNE Research has conducted an analysis on key patents regarding LTO-based anode material of lithium-ion secondary battery. By

providing key patent analysis containing patent technology, management and patent rights, information and solution for prior

technology, prior technology problem, related technology flow, readers can obtain new ideas and prevent and prepare for patent

dispute problem in advance through third-party assurance.

The following report analyzes 1,106 valid patents which are screened out from 9,352 patents regarding LTO-based anode material of

lithium-ion secondary battery, published in Korea, US, Japan and European countries until December 2012. The report will guide the

readers on patent trends and key patents of LTO-based anode material of lithium-ion battery.

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Patent Analysis ScopeThis report provides patent analysis on LTO-based anode material which are important for rapid charging as following.

Patent Search Period : PCT patents and patents registered and disclosed in Korea, US, Japan, and Europe until 2012. 12. 18

Patent Search Scope : Selected by keyword extraction from patent titles, summaries, technology classification and patent

content on country to country basis.

To avoid omission separate search has been conducted for major patent applicants.

Search Period Registered and Disclosed Patents until 2012. 12.18

Search Country US, Japan, Europe, PCT, Korea

Major ApplicantTOSHIBA, PANASONIC, SANYO, GS YUASA, SAMSUNG SDI, LG CHEMICAL, MEDTRONIC,

TOHO TITANIUM, TOYOTA MOTOR HYDRO-QUEBEC, SUD-CHEMIE AG, CEA

Technology Sector

Search Formula

※ Only representative search formula has been shown above of repetitive keyword search using different formula for applicants of each leading company.

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The report is composed in the order of Patent Search, Valid Patent Extraction, Patent Application Trend Analysis, Key Patent

Selection and Summary Analysis, Key Patent In-depth Analysis and Conclusion/Implication.

• Search Period : ~ 2012.12.18

• Search Country : KR, JP, US, EP, PCT *

• Search DB : KIWEE, KIPRIS, FOCUST

Patent Search /Valid Patent Extraction

Key Patent Analysis of Leading Company

Patent Application Trend Analysis

• Patent application status by technology/country/year.

• Patent application status by technology/applicant.

Conclusion / Implication

• Patent trend analysis results.

• Development cases of patent technology in issue.

• Implication

Key Patent Selection /Summary Analysis

• Understand key patent selection/summary.

• List summary of key patent.

Expected Effect

- Understand technology/market trend- Discover research theme/

Establish development strategy- Submit patent application/

Establish patent strategy/Prevent patent dispute

- Create business opportunities, etc.※ PCT : Patent Cooperation Treaty


• Key patent analysis of major companies.

• Major companies : Toshiba, Altairnanoetc.

• Technology transfer cases of University/Research Institute.Report

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Technology Overview

Overview of Anode Technology

Overview of Lithium Titan Oxide (Li₄Ti₅O₁₂)

Anode Material Technology Development Trend

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Overview of Lithium Titan Oxide (Li₄Ti₅O₁₂)Among oxide anode material, spinel structured Li₄Ti₅O₁₂ (LTO) is receiving the most attention as a material for batteries

used in vehicle and power storage devices due to the properties of excellent output power, rapid charging ability and

stability.

The voltage of LTO is flat and the current capacity is 170mAh/g which is less than half of carbon anode’s 370mAh/g but

insertion current is 1.5V, higher than 0.05V of carbon anode. LTO shows excellent cycle characteristic having less than 1%

charge and discharge volume expansion and does not form SOE(Solid Electrolyte Interface) since electrolyte

decomposition does not occur.

LTO also has low-temperature characteristic, high charge and discharge rate and high thermal stability and therefore is

mounted in plug in hybrid electrical vehicle. If the major problem of energy capacity decrease can be resolved, LTO will be

the most suitable candidate for vehicle and energy storage device which can be rapidly charged, manufactured in

relatively low price and which safety can be secured.

[Particle of Li₄Ti₅O₁₂] [Li₄Ti₅O₁₂ Spinel Structure] [Li₄Ti₅O₁₂ Charge and Discharge Curves]

Capacity/mAhg

Voltag

e/V. vs. Li/Li+

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Anode Material Technology Development TrendMost of lithium-ion secondary batteries commercialized today use the original anode and electrolyte material but the

cathode material LiCoO₂ is replaced by LiFePO₄. Since LiFePO₄ is safer and affordable than LiCoO₂, it is possible to

improve the reliability of the battery and reduce the production cost.

However, if the practice of using carbon material as anode and lithium salt dissolved electrolyte as organic solvent

continues it will be difficult to ensure the overall safety of lithium-ion secondary battery.

[Technology Roadmap for Lithium-ion Secondary Battery]

(Source : E-Co Pro)

Battery Assembling Technology Material Technology Innovative Technology

Limited material pool- LiCoO2/Graphite

Competition based of Assembly Technology

- Efficient use of space- High loading design

Technology diversification- Increasing importance of

patents on core technology- Cathode LiCoO2 ⇒ NCM

Competition on high performance, low cost material technology

High Capacity, Long Life, High Safety, Low Cost,

1st Gen 2nd Gen 3rd Gen

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Patent Application Trend Analysis


Patent Search Results and Selection of Validated Patents

Patent Application Trend by Country/Year

Major Patent Applicants by Country

TOP10 Patent Applicants

Patent Application Trend by Technology

Patent Application Trend by Technology/Year

Patent Application Trend by Technology/Applicant

Technology Status by Period of Application

Concentrated Patent Technology by Country

Patent Application Distribution of Major Applicants by Technology

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Technology ClassificationFor analysis, the patents were classified into technology of Lithium Titan Oxide Composition, Lithium Titan Oxide Metal

Substitution, Lithium Titan Oxide Surface Structure, Lithium Titan Oxide Particle Size Distribution, LTO Electrode Fabrication,

Cell/Pack Manufacturing and Battery Application as shown in the following table.

Technology Classification Main Keyword

LTO*

LTO-based Battery

*LTO: Lithium Titan Oxide, Molecular Formula: Li₄Ti₅O₁₂*ESS: Energy Storage System

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Patent Search Results and Selection of Validated Patents By repeating different search formulas of keywords including major companies, 9,351 number of data were obtained and

after removing duplicated patents and noise from the data, 1,106 validated patents of LTO anode material were extracted.

The patents are classified by technology and country as follows.

Country


TotalComposition

MetalSubstitution

Particle Size Distribution

SurfaceStructure

LTOElectrode

Cell/Battery Pack

Application Others

US

JP

PCT

EP

KR

RelatedPatent

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Patent Application Trend by Country/YearThe patent application trend by country and year is shown in the following graph. The application started from 1997 and

increased until 2010. The number of patent application is highest in US followed by Japan, Korea, PCT and Europe. US and

Japan are particularly showing high proportion of patent application.

0

20

40

60

80

100

120

140

160

180

1997 1998 1999 2000 2001 2002 2003 2004 2005 2006 2007 2008 2009 2010 2011 2012

Year JP EP PCT US KR

US, 359, 33%

PCT, 118, 11%

EP, 78, 7%

JP, 343, 30%

KR, 208, 19%

InvalidPeriod

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Major Patent Applicants by Country Toshiba, Medtronic, LG Chem. Sanyo, Samsung SDI, Panasonic, Toyota and Hydro-Quebec tend to have a high share of

patents in most countries.

0 10 20 30 40 50 60

TOSHIBA

Medtronic

LG CHEM

SAMSUNG SDI

CEA

Hydro-Quebec

SANYO

Panasonic

US

0 10 20 30 40 50 60

TOSHIBA

SANYO

SAMSUNG SDI

Panasonic

TOYOTA

Hydro-Quebec

Kyocera

SUMITOMO

JP

0 10 20 30 40 50 60

Panasonic

LG CHEM

Toho Titanium

TOSHIBA

CEA

Medtronic

SUMITOMO

TOYOTA

EP

0 10 20 30 40 50 60

LG CHEM

SAMSUNG SDI

Medtronic

TOSHIBA

KAIST

Panasonic

Hydro-Quebec

SÜD-Chemie AG

KRReport

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Key Patent Analysis

Key Patent Analysis Overview- Key Patent Selection Method - Key Patent Selection Status- Key Patent Application Distribution by Year- Key Patent Application Distribution by Applicant/Technology- Key Patent Status of Major Applicants by Technology- Key Patent Status by Company- Key Patent Technology Flowchart

Key Patent Analysis by Major Companies- Toshiba- Medtronic- Toho Titanium- Altairnano- Panasonic- CEA- LG Chemical- EnderDel- Hydro-Quebec- Sanyo / GS Youasa- SUD-Chemie- Others

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Key Patent Selection Method 114 number of key patents were selected among 1,106 validated patents related to LTO-based anode material by patent

index review.

Patent

Index

Patent

Index

Total of 114 Key Patents

Scalability : Foreign Patent Application - Family Patent＊ Citation : Forward, Backward Patent Rights-Legal Status : Registration, Pending, Invalid, Expire Conformance : Technology Conformance Prior Application : Application Date, Priority Date Period of Rights Number of Independent/Dependent Claims : Number of Implementation

Key Patent Analysis Procedure

Key Patent AnalysisKey Patent Selection Key Patent In-depth Analysis

Patent Index Review

Key Patent Selection

Key Patent Summary Analysis

- Novelty, Progressivity,

Effectiveness, etc.

Patent Technology Applications

Analysis on Patent Technology

in Issue

Citation Analysis

Key Patent Selection Method

*Family Patent : A set of patent taken in various countries to protect a single invention, by a common inventor※Patent Index : Objective index to determine the importance of patent by foreign patent application, patent citation and others.

Selected by order of

priority of patent index.

OrderOf

Priority

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Country

LTO Anode Material & Manufacturing Method

TotalToshiba Medtronic

Toho Titanium

Altairnano Panasonic CEA LG Chem TOYOTA Others

US

JP

PCT

EP

KR

Total

The selected 114 key patents are as follows

Key Patent Selection Status

* Key patents were selected and analyzed by giving first priority to US patents.

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Key Patent Technology Flowchart

~2000 2001 2002 2003 2004 2005 2006

Toho Titanium Sion Power Altair Nanomaterials Panasonic Panasonic Toyota Motor Panasonic

ASAHI GLASS Hydro-Quebec CEA ALTAIRNANO

US10000090768269 20010125

Toho Titanium Samsung SDI

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Key Patent Technology Flowchart

2007 2008 2009 2010 2011 2012

Hydro-Quebec Hydro-Quebec Medtronic, Inc. Toshiba 3M

CEA SUD-CHEMIE SAMSUNG SDI Medtronic, Inc.KAIST

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Key Patent List - Toshiba The status of selected key patents are listed in the following table by the order of leading company withToshiba coming first.

NO Patent NO

Application NO

Application Date Title Applicant Family Technology

Classification

1 US007803483

US100000110260435 20051028

Hermetically sealed high cap acity nonaqueous electrolyte battery and battery pack with the same

Toshiba

JP004208865B2_20090114 | JP2007000018881A_20070125 | KR10000749198B1_20070813 | KR102007000006593A_20070111 | US2007000009794A1_20070111 | CN20071893168A_20070110 | CN2009100524933C_20090805 |

MetalSubstitution

2 US008137843

US100000110853546 20070911

Negative electrode active ma terial for nonaqueous electrolyte battery, nonaqueous electrolyte battery, battery pack, and vehicle

Toshiba

JP004602306B2_20101222 | JP2008000091079A_20080417 | KR10000895554B1_20090429 | KR102008000029878A_20080403 | US2008000078594A1_20080403 | CN2008101154729A_20080402 | CN2009100573983C_20091223 |

SurfaceTreatment

3

4

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NO PatentNO.

Application NO

Application Date Title Applicant Family Technology

Classification

5

6

7

8

9

10

Key Patent List - Toshiba

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Title

Assignee Country US

Inventor Legal Status Patented

Patent Families

Application No. US100000110260435 Publication NO. US007803483B2 Patent No. US007803483

Application Date 20051028 Publication Date 20100928 Patent Date 20100928

Abstract

Claims

A nonaqueous electrolyte battery includes a positive electrode, a negative electrode and a case formed of a film and including a heat sealedsection formed on at least one edge portion of the case. The negative electrode contains a negative electrode active material having a lithiumion insertion potential not lower than 0.4V (vs. Li/Li+). The nonaqueous electrolyte battery also includes positive and negative electrodeterminals. A first alumina layer having projections and recesses is formed on at least one part of a seal portion of the positive electrodeterminal. A second alumina layer having projections and recesses is formed on at least one part of a seal portion of the negative electrodeterminal. Further, the positive and negative electrode terminals have a cross sectional area S (mm2) which satisfies 0.6Q≦S≦2Q.

1. A nonaqueous electrolyte battery, comprising:

a case formed of a film and including a heat sealed section formed on an edge portion of the case;a nonaqueous electrolyte provided in the case;a positive electrode provided in the case and containing a positive electrode current collector formed of an aluminum foil or an aluminum alloyfoil;a negative electrode provided in the case and containing a negative electrode active material having a lithium ion insertion potential not lowerthan 0.4 V (vs. Li/Li+), and the negative electrode containing a negative electrode current collector formed of an aluminum foil or an aluminumalloy foil;a positive electrode terminal including a tip portion withdrawn to an outside of the case via the heat sealed section of the case, and a sealportion being positioned in the heat sealed section, and the positive electrode terminal being made of aluminum or aluminum alloy andelectrically connected to the positive electrode;a first alumina layer having projections and recesses and formed on the seal portion of the positive electrode terminal;a negative electrode terminal including a tip portion withdrawn to the outside of the case via the heat sealed section of the case, and a sealportion being positioned in the heat sealed section, and the negative electrode terminal being made of aluminum or aluminum alloy andelectrically connected to the negative electrode; anda second alumina layer having projections and recesses and formed on the seal portion of the negative electrode terminal,wherein the positive electrode terminal and the negative electrode terminal have a cross sectional area S (mm2) which satisfies the formula(1) given below:

Hermetically sealed high capacity nonaqueous electrolyte battery and battery pack with the same

Kabushiki Kaisha Toshiba

Norio Takami | Hiroki Inagaki

JP004208865B2_20090114 | JP2007000018881A_20070125 | KR10000749198B1_20070813 |KR102007000006593A_20070111 | US2007000009794A1_20070111 | CN20071893168A_20070110 |

CN2009100524933C_20090805 |

Key Patent Analysis - Toshiba

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Title

Assignee Country US

Inventor Legal Status Patented

Patent Families

Application No. US100000120691365 Publication NO. US007829224B2 Patent No. US007829224

Application Date 20100121 Publication Date 20101109 Patent Date 20101109

Abstract

Claims

A nonaqueous electrolyte battery includes a negative electrode including a current collector and a negative electrode active material having aLi ion insertion potential not lower than 0.4V (vs. Li/Li+). The negative electrode has a porous structure. A pore diameter distribution of thenegative electrode as determined by a mercury porosimetry, which includes a first peak having a mode diameter of 0.01 to 0.2 μm, and asecond peak having a mode diameter of 0.003 to 0.02 μm. A volume of pores having a diameter of 0.01 to 0.2 μm as determined by the mercuryporosimetry is 0.05 to 0.5 mL per gram of the negative electrode excluding the weight of the current collector. A volume of pores having adiameter of 0.003 to 0.02 μm as determined by the mercury porosimetry is 0.0001 to 0.02 mL per gram of the negative electrode excluding theweight of the current collector.

1. A nonaqueous electrolyte battery, comprising:

a positive electrode,a negative electrode including a current collector and a negative electrode layer being supported by the current collector, and the negative electrode layercontaining a l ithium‐titanium oxide; anda nonaqueous electrolyte;wherein:the negative electrode has a porous structure;a pore diameter distribution of the negative electrode as determined by a mercury porosimetry, which includes a first peak having a mode diameter fall ingwithin a range of 0.01 to 0.2 μm, and a second peak having a mode diameter fal l ing within a range of 0.003 to 0.02 μm;a volume of pores having a diameter of 0.01 to 0.2 μm as determined by the mercury porosimetry is 0.05 to 0.5 mL per gram of the negative electrode excludingthe weight of the current collector; anda volume of pores having a diameter of 0.003 to 0.02 μm as determined by the mercury porosimetry is 0.0001 to 0.02 mL per gram of the negative electrodeexcluding the weight of the current collector.

Nonaqueous electrolyte battery, battery pack and vehicle

Kabushiki Kaisha Toshiba

Hiroki Inagaki | Norio Takami

JP004213688B2_20090121 | JP2007000018882A_20070125 | KR10000749197B1_20070813 |KR102007000006592A_20070111 | US007662515B2_20100216 | US007972730B2_20110705 |

US2007000009801A1_20070111 | US2010000119936A1_20100513 | US2011000020699A1_20110127 |US2011000229758A1_20110922 | CN20071893167A_20070110 | CN2009100463285C_20090218 |

Key Patent Analysis - Toshiba

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Technology to Overcome LTO Limitations

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Anode active material which the aspect ratio of MoOx is less than twice of cathode material.

– Ellipsis –– Ellipsis –

The development of MoOx anode material of Sanyo is shown in the following.

The technology mixes high energy density active material molybdenum dioxide with other metals and use it as a material for anode.

– Ellipsis –

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NOPatent

NOApplication

NOApplication

DateApplicant Title

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