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中国废旧电池的回收与再利用技术现状


US-China Electric Vehicles and Battery Technology Workshop, China 2011

中国废旧电池的回收与再利用技术现状
Current situation of recycling and reusing for spent batteries in China 李 丽 北京理工大学

/>Li Li Beijing Institute of Technology
E-mail: lily863@bit.edu.cn

US-China Electric Vehicles and Battery Technology Workshop, China 2011

内容提要 Outline
1

我国目前的废旧电池回收现状
The current status of spent battery recycling in China

2

废旧电池综合回收利用技术
Recycle and recovery technologies of spent batteries

3

国内典型电池回收企业
Typical battery recycling companies in China
Beijing Institute of Technology

US-China Electric Vehicles and Battery Technology Workshop, China 2011

Challenge and Opportunites of Power Battery 1.Performance and Safety 2.Cost Reduction 3.Battery Recycling
From the viewpoints of environmental preservation, recovery of major components or valuable resources, and provision of raw materials, the battery recycling is highly desirable inInstitute ofpresent time or the future. Beijing either the Technology

“中国废旧电池回收体系”是在政府的规范引导下、通过 多种渠道、多种方式、集合多种社会多种资源体,所共同 搭建起的一种可以将废旧电池有效环保回收、无害化处理、 资源化再生,并能自我存续和持续固定的一种资源循环利 用体系模式。
Under the guidance of the government’s regulations and specifications, wasted battery recycling system in China is a self-survival and continued fixed resource recycling system model . It supplies an effective way to recycle, reduce and reuse for wasted batteries.

Beijing Institute of Technology

根据回收所针对的主体的不同,可分为“上游”和“下游”两类
According to different recycle subjects, it can be divided into "upstream" and "downstream”

上游-电池生产企业 生产过程中所产生 的不良品、报废品、召 回品等废旧电池的回收 处理问题;上游回收以 商业模式为基础。
Upstream – battery manufacturers Defective products, scrap and recalled products arising from production process, and other issues of recycling; Business Model

Beijing Institute of Technology

根据回收所针对的主体,可分为“上游”和“下游”两类
According to different recycle subjects, it can be divided into "upstream" and "downstream”

下游-电池消费者 使用报废之后的废旧 电池回收处理问题;下 游回收以公益模式为基 础,以社会公德、责任 心为依归,是社会文明 进步的表现。
Downstream - Battery consumers wasted battery recycling issues after degradation; Public Service It depends on social ethics, social civilization and progress.

Beijing Institute of Technology

US-China Electric Vehicles and Battery Technology Workshop, China 2011

我国锂离子电池产量
Production of LIB in China

DATA FROM: CHINA BATTERY INDUSTRY ASSOCIATION

Beijing Institute of Technology

US-China Electric Vehicles and Battery Technology Workshop, China 2011

锂离子电池的使用量和废弃量
World production and consumption of LIBs

2000年5亿只 500million units

2004年9亿只 900million units

2010年46亿只 4.6billion units

使用年限2年 年平均废弃量200-500吨 Amount of waste:200-500t/y
Beijing Institute of Technology

US-China Electric Vehicles and Battery Technology Workshop, China 2011

Dry batteries

?

Button batteries

Ni/MH batteries

Beijing Institute of Technology

Li-ion batteries

US-China Electric Vehicles and Battery Technology Workshop, China 2011

2001年《危险废物污染防治 技术政策》Technology policy 1997年《关于限制电池产品汞含 量的规定》Limitation of Mercury
Content for Batteries of pollution control for hazardous wastes

2002年《关于涉汞行业环境保 护管理规定》Environmental
protection regulations for Industries concerning mercury

2001 1997

2002

1995年 《无汞干电池》 1995
Mercury-free batteries

中国 China
2006 2009

2003
2003年《废电池污染防治 技术政策》Pollution
prevention and technology policy for spent battery

2010
2010年《废弃电器电子产品 回收处理管理条例》
Regulations for recycling of waste electrical and electronic products

2009年《一次废旧电池分类》 和《二次小型电池废料废件 分类》推荐性国家标准
Recommended National Standards of the classification of waste dry battery and second battery

2006年《电池行业清洁 生产评价指标体系(试 行)》Clean production
evaluation system for battery industry

Beijing Institute of Technology

废旧电池产生的危害
Safe disposal may become a serious problem due to the presence of flammable and toxic elements or compounds

重金属污染
Heavymetals

危害
有机溶剂污染 Organic solvents

Hazards

大气污染 Air pollution

Beijing Institute of Technology

US-China Electric Vehicles and Battery Technology Workshop, China 2011

废旧电池污染防治的原则
Principles of pollution control for spent battery

全过程控制 避免二次污染和污染转移 total process control system

减量化、资源化和无害化 Reduce,Reuse,Recycle

突出重点、分类控制 Target key points, classified control

Beijing Institute of Technology

US-China Electric Vehicles and Battery Technology Workshop, China 2011

废旧二次电池回收处理技术
Processes and technologies for the recycling of spent batteries
酸浸过程(Acid leaching) 生物淋滤(Bioleaching) 化学沉淀法(Chemical precipitation) 溶剂萃取法(Solvent extraction) 电化学法(Electrochemical process)

直接合成电极材料
Direct synthesis of electrode materials

化学法
Chemical treatment

溶胶凝胶法(Sol-gel method) 水热法(Hyrdothermal method) 共沉淀法(Co-precipitation method) 电化学法(Electrochemical method)

物理法
Physical treatment
火法(Thermal treatment) 机械分离(Mechnical separation process) 研磨过程(Mechanochemical process) 有机溶剂溶解(Dissolution process)

Beijing Institute of Technology

Summary of recycling processes or treatment methods for the components of lithium-ion batteries

A single recycling process can only achieve the destination of recovering a part of components or can only be one step of a whole procedure for recycling spent LIBs. Therefore, combination of several single recycling processes is necessary to recycle or recover the main components from spent LIBs.

Beijing Institute of Technology

US-China Electric Vehicles and Battery Technology Workshop, China 2011

(1)物理法(预处理)

Physical method (Pretreatment)

工艺简单 Simple process

成本低 Low cost

物理法

Skinning, crushing, removing of crust, sieving and separation
(density, conductivity, magnetic behavior etc)

能耗大 Large energy consumption

易引起污染
Environmental Pollution

Beijing Institute of Technology

US-China Electric Vehicles and Battery Technology Workshop, China 2011

机械研磨法 Mechanochemical process
Co-grinding of LiCoO2 with polyvinyl chloride(PVC)

钴酸锂材料 与PVC共研 磨

研磨后Co和 Li与PVC中 的氯生成无 机氯盐

Formation of Liand Co-chlorides

用水溶解, 可与其他研 磨物质分离

Water leaching

90%Co & almost 100%Li can be recovered. About 90% of chlorine in PVC sample transformed into inorganic chlorine.

Beijing Institute of Technology

US-China Electric Vehicles and Battery Technology Workshop, China 2011

(2)化学法 Chemical processes

化学处理法
Chemical processes

酸浸或生物淋滤
Acid leaching Bioleaching

沉淀法 (Chemical precipitation)

溶剂萃取法 (Solvent extraction)

电化学法 (Electrochemical process)

Beijing Institute of Technology

一、天然有机酸对钴酸锂电极材料的浸出研究 (1)柠檬酸对钴酸锂电极材料的浸出研究
Leaching process for LiCoO2 materials using citric acids as leachant

Spent LIBs from cellular phones

Li

Co

Mn

Ni

Beijing Institute of Technology

Fig. Flowsheet of the hydrometallurgical recycling process for lithium ion secondary rechargeable batteries.

T m =90 C, Time=30min

o

T m =90 C, Time=30min

o

(a)

100

(b)
%

100 80 60 40 20
% Leaching Effic iency /

80 60 40 20 0 60 100 50
Le ac

Leaching Effici ency /

40
h in

80 60 40 10 20 0
Le ac hi ng Te m p a er tu

re

/oC

30 20 gT im e/ mi n

60
Le

50
h in

ac

40

80 30 60 40 10 20 0
Le a i ch ng Te m

0 100 / o C e
ra tu r

gT im

20 e/ mi n

pe

Fig. 6. Effect of leaching temperature and leaching time on the leaching of waste LiCoO2 with 1.25 M citric acid

100

100

Leaching efficiency (%)

80 60 40 20 0

Leaching efficiency (%)

80

60

Co Li

40

Co Li

20 0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6

5

10

15

20

25

30
-1

35

40

45

Soild/Liquid (g L )

Concentration of citric acid (M)

Fig. 7. Effect of solid/liquid ratio on the leaching of waste LiCoO2 with 1.25 M citric acid at 90 °C for 30 min

Beijing Institute of Technology

Fig. 8. Effect of citric acid concentration on the leaching of waste LiCoO2 at 90 °C for 30 min L.Li, J. Ge, F. Wu et al ,J. Hazard. Mater.176 (2010), pp. 288-293

19

(2)苹果酸对钴酸锂电极材料的浸出研究
Organic acid leaching using malic acids

Fig. 1. SEM images of different cathode materials: (a) the dismantled cathodic material from a spent LIB, (b) the cathodic material after treatment with NMP, (c) the cathodic material after dismantling and calcination at 700 °C for 5 h and (d) the leach residues.

Fig. 2. Flow sheet for the recovery of Co and Li from spent Li-ion batteries using DL-malic acid as a leachant

Beijing Institute of Technology

20

(2)苹果酸对钴酸锂电极材料的浸出研究

(a)

Tm=90 C, time=40min 100

o

(b)

Tm=90 C, time=40min 100

o

y (%)

80

60

leaching efficienc

60 40 20 100 50 40 30 60 20 40 10 20 80
o ) (C

40

20 50 40 100 30 80 20 60 10

le a

ch

ing

t im

e(

mi

n)

C) re ( 20 a tu per te m
o

40

le a

chi

ng

tim

e ( m in )

p te m

e ra

e tur

Fig. 6. Effect of leaching temperature and leaching time on the leaching of waste LiCoO2 with 1. 5 M malic acid (H2O2=2.0 vol.%., S:L= 20 gL?1 and agitation speed=300 rpm) leaching efficiency of Li and (b) leaching efficiency of Co.

(Using 1.5 M DL-malic acid, 2.0 vol.% hydrogen peroxide, a leaching temperature of 90 ℃, a S:L ratio of 20 g/L and a time interval of 40 min nearly 100 wt.% Li and more than 90 wt.% Co were extracted.

BeijingLiInstitute of Technology Li, Jing Ge, Feng Wu et al , Waste Management, 2010,30: 2615-2621

leaching efficenc

y (%)

80

三、生物淋滤技术

Bioleaching process

? Bio-hydrometallurgical processes have been gradually replacing the hydrometallurgical one due to their higher efficiency, lower costs and few industrial requirements. ? Using special bacteria which utilized elemental sulfur and ferrous ion as energy source to produce metabolites like sulfuric acids and ferric ion in the leaching medium.

生物淋滤--液膜萃取法工艺流程

Morphology

Beijing Institute of Technology

固液比和硫源浓度对金属离子的生物溶释效率影响
Effect of S/L and Sulfur concentration on leaching efficiency of metals in Bio-leaching
700

Li的溶出浓度(mg/L)

2200

Co的溶出浓度(mg/L)

600 500 400 300
1% 2% 4%

2000 1800 1600 1400 1200
1% 2% 4%

200 0 2 4 6 8 10 12 14

1000 0 2 4 6 8 10 12 14

淋滤时间/d

淋滤时间/d

560

2400

Li的溶出浓度(mg/L)

520 480 440 400 2 4 6 8 10 12 14

Co的溶出浓度(mg/L)

2200 2000 1800 1600 1400 1200
1g/L 2g/L 4g/L

1g/L

2g/L

4g/L

淋滤时间/d

2

4

6

8

10

12

14

Beijing Institute Bioresource Technology,100 :6163–6169,2009. of Technology

淋滤时间/d

US-China Electric Vehicles and Battery Technology Workshop, China 2011

国内典型电池回收企业-1
Typical battery recycling companies in China-1 深圳市格林美高新技术股份有限公司 Shenzhen Green Eco-manufacture Hi-tech Co., Ltd

废旧电池回收再生工艺流程图
The flowchart of recycling process for spent batteries

Beijing Institute of Technology

Beijing Institute of Technology

US-China Electric Vehicles and Battery Technology Workshop, China 2011

国内典型电池回收企业-2
Typical battery recycling companies in China-2 佛山邦普镍钴技术有限公司 FUOSHAN BANGPU NI/CO HIGH-TECH CO.,LTD

废旧电池资源桥接式循环演示中心 Demonstration center of recycling process for spent batteries

Beijing Institute of Technology

Beijing Institute of Technology

Beijing Institute of Technology

US-China Electric Vehicles and Battery Technology Workshop, China 2011

国内典型电池回收企业-3
Typical battery recycling companies in China-3

泰力废旧电池回收技术有限公司
SHENZHEN TAILI WASTE BATTERY RECYCLE. CO.,LTD

Cobalt Sulfate lithium carbonate.

It is still necessary to develop an efficient collection system in order to receive the spent LIBs consumed around the worldTechnology the spent LIBs. Beijing Institute of and recycle

Thanks for your attention!

?

This work is supported by the 973 Program . ? Email: lily863@bit.edu.cn

Beijing Institute of Technology


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